Functional materials for use in optical systems

ABSTRACT

Functional optical materials for optical systems that are typically useful in optical waveguides, optical switching systems, optical modulators, optical computing systems and the like. Included are polymer systems and electrooptical chromophores. Polymers are thermoplastic and/or thermosetting polymers and are blended or co-polymerized with the electrooptic chromophore. The thermoplastic or thermosetting polymer selected from an acrylic/methacrylic, polyester, polyurethane, polyimide, polyamide, epoxy resin, or hybrid (organic-inorganic) or nanocomposite polyester polymer. The electrooptic chromophore is selected from a substituted aniline, substituted azobenzene, substituted stilbene, or substituted imine. Methods for improving adhesion promotion for the various novel materials are also provided.

FIELD OF THE INVENTION

[0001] The field of this invention is functional materials useful inoptical systems exemplified by, but not limited to, optical switches,modulators, and other devices that are compatible with silica ornon-silica waveguides.

BACKGROUND OF THE INVENTION

[0002] A waveguide is any structure which permits the propagation of awave through its length despite diffractive effects, and possiblecurvature of the guide structure. An optical waveguide is an opticalstructure capable of guiding a beam of laser light along light channelsin the waveguide, and is defined by an extended region of increasedindex of refraction relative to the surrounding medium. The waveguidetypically includes both the light channels in which light wavespropagate in the waveguide, and surrounding cladding which confine thewaves in the channel. The strength of the guiding, or the confinement,of the wave depends on the wavelength, the index difference, and theguide width.

[0003] Discrete control of the refractive index of a given polymer isnecessary for creating silica or non-silica waveguide optical switchcomponents; however, it is not the only property which determines thedurability and efficiency required for a commercial product. The presentinvention demonstrates that there is a critical interplay between thepolymer, the silica substrate, the electrodes and the electro-opticmaterial which must be elucidated to create a commercially viableproduct.

[0004] Bosc et al., describes the use of two fluorinated monomers (1H,1H, 2H, 2H tridecafluoro-octyl methacrylate and trifluoroethylmethacrylate) to create copolymers having refractive index valuesbetween 1.370 and 1.403 at 1.3 um (Design and Synthesis of LowRefractive Index Polymers for Modulation in Optical Waveguides, OpticalMaterials Vol 13 (1999), pp. 205-209). Bosc et al. further discusscopolymerization of an electro-optic monomer, methacrylic acid ester ofDisperse Red 1 (the refractive index for a homopolymer of this materialis 1.710). These monomers were blended to achieve a final terpolymerrefractive index of 1.5. The Tg of these systems varied between 82° C.and 92° C. While these compositions allow (possess) some degree ofoptical modulation, they are not suitable for use in an optical switchwhich meets the reliability and efficiency requirements of commercialcommunications networks.

BRIEF DESCRIPTION OF THE INVENTION

[0005] These and other deficiencies of the prior art are overcome by thepresent invention, which provides both polymer systems and electroopticchromophores that form the components of a optical devices such asoptical switches or modulators and other devices useful in an opticalwaveguide.

[0006] The polymer component is a thermoplastic or thermosetting polymerwhich is blended or co-polymerized with an electrooptic chromophore. Thethermoplastic or thermosetting polymer is typically selected from thegroup consisting of acrylics/methacrylics, polyesters, polyurethanes,polyimides, polyamides, polyphosphazenes, epoxy resins, and hybrid(organic-inorganic) or nanocomposite polyester polymers. Combinations ofthermoplastic and thermosetting polymers (interpenetrating polymernetworks) are also envisioned as part of this invention.

[0007] Additionally, the thermoplastic and/or thermosetting polymertypically has a glass transition temperatures above 100° C., oneembodiment for low index materials has a refractive index valuesless-than 1.5 while another embodiment for high index materials hasrefractive index values greater than 1.5. The polymers are combined withchromophores, either as part of the backbone chain or blended andtypically contain compatibilization additives or groups and/or adhesionpromotion additives or groups. The electrooptic chromophore according tothe invention is typically a substituted aniline, substitutedazobenzene, substituted stilbene, or substituted imine with one or moreas further defined below.

BRIEF DESCRIPTION OF THE DRAWING

[0008] The Drawing illustrates a schematic for one embodiment of theinvention where a material according to the invention is used to controllight passing through a fiber optic waveguide in response to temperaturechanges.

DETAILED DESCRIPTION OF THE INVENTION AND BEST MODE

[0009] A functional optical material is any optical material thatchanges its index of refraction or other selected optical property inresponse to its environment. Examples of changes in the environmentinclude but are not limited to changes in an electrical field, changesin a magnetic field, changes in temperature, changes in pressure.

[0010] This invention broadly discloses functional optical materialsand/or their applications that relate to optically active chromophores.An optically active chromophore is any molecule or chemical group whichchanges its index of refraction or produces a change in the index ofrefraction of a compound or composition containing it, upon a change inthe environmental conditions in which it is placed. More specifically,the invention discloses compounds and/or their uses that relate toelectrooptic chromophores, thermooptic chromophores and magnetoopticchromophores. Electrooptic chromophore—any molecule or chemical groupwhich changes its refractive index or produces a change in therefractive index of a compound or composition containing it uponapplication of an electric field. Thermooptic chromophore—any moleculeor chemical group which changes its refractive index or produces achange in the refractive index of a compound or composition containingit upon a change in temperature. Magnetooptic chromophore—any moleculeor chemical group which changes its refractive index or produces achange in the refractive index of a compound or composition containingit upon application of a magnetic field.

[0011] The present invention provides both polymer systems and opticallyactive chromophores that form the components in optical systems such asan optical switch useful for in an optical waveguide.

[0012] Precursor materials unless specifically labeled otherwise are inweight percent (wt. %). All measured index of refractions listed hereinare measured at about 20° C., and at wavelengths at the Sodium d line,about 589 nm, unless labeled otherwise.

[0013] As used herein, “glass transition temperature” or T_(g) refers tothe temperature in a polymer at which a hardened polymer shows atransition toward more mobile polymer chains as evidenced by dielectricspectroscopy.

[0014] The term “backbone” or “polymer backbone” as used hereinindicates the extended linear repeating chain of a polymer.

[0015] The typical molecular weight range (number average) of polymersof this invention is between about 5,000 to about 5,000,000. Preferablythe polymers of the invention have a molecular weight range betweenabout 7,000 to about 500,000. Most preferably, the polymers of thisinvention have a molecular weight range of about 10,000 to about 30,000.

[0016] I. Polymer Systems

[0017] The polymers of this invention are thermoplastic (i.e., melt-flowor are solvent soluble), thermosetting in nature (i.e., resist meltingand are not soluble in solvents), or are a combination of thermoplasticand thermosetting polymers (interpenetrating polymer networks).

[0018] Additionally, the polymers of this invention typically have glasstransition temperatures above 100° C. The refractive index values ofthese polymeric compositions typically vary between about 1.3 to about≦1.5 in one embodiment; and from about 1.5 to about 1.8 in a secondembodiment. Typically, the polymers of the present invention can contain(part of the backbone structure) between 0.1 and 10% of an adhesivepromotion group or combination of groups such as silane, carboxylicacid, nitrile, or hydroxyl functional groups. Additionally, all of thepolymers can be either blended with an EO chromophore or can have the EOchromophore covalently attached to the polymer backbone structure.

[0019] Thermoplastic polymers are polymers that soften or become plasticwhen they are heated. The process of heating and cooling such polymerscan be carried out repeatedly without affecting any appreciable changein the properties of the polymers. After thermoplastic polymers aresynthesized, they can be dissolved in a solvent and applied to surfaces.Additionally, these polymers can be heated causing them to melt flow andgenerally develop strong adhesive bonds to a substrate.

[0020] Thermosetting polymers include polymer materials in whichchemical reactions, including cross-linking, occur while the resins arebeing molded. The appearance and chemical and physical properties of thefinal product are entirely changed, and the product is resistant tofurther applications of heat (up to the charring point). Thethermosetting polymers of the present invention are structurally definedas three dimensional crosslinked chains or polymeric network structures.

[0021] A primary difference between thermoplastic polymers andthermosetting polymers is that thermoplastic polymers are capable ofmelting and reflowing, and are soluble in solvents. Thermosettingpolymers, after they are cured or crosslinked, are not soluble insolvents and will not reflow when heated. Combinations of thermoplasticand thermosetting polymers (interpenetrating polymer networks) are alsoenvisioned as part of this invention.

[0022] The chemistry of thermoplastic and thermosetting polymer systemsincludes the following preferred materials and reactions;

[0023] (a) acrylic thermoplastic polymers containing functional groups(double bonds, epoxides, alcohols, acids) capable of entering intosecondary chemical reactions that create three dimensional networkstructures that are solvent insoluble or will not melt and reflow uponheating;

[0024] (b) polyurethane polymers based on diisocyanates andmultifunctional alcohols that react to create three dimensional networkstructures that are not soluble in solvents;

[0025] (c) polyesters that contain unsaturated sites in their backbonestructure or contain acid/hydroxy functional groups that can bechemically reacted with other similar multifunctional crosslinkingagents to create three dimensional network structures;

[0026] (d) epoxy resins that can be reacted with polyamides,polymercaptans or polyacids to create three dimensional structures; and

[0027] (e) polyphosphazenes and polysiloxane systems can also beprepared to contain multiple vinyl unsaturation sites that can be curedwith peroxides or other free radical addition initiation mechanisms tocreate three dimensional structures.

[0028] A broad embodiment of the invention includes the following:

[0029] A. For a low refractive index optical system (e.g. silica basedoptical waveguide systems): selecting and reacting one or more monomershaving a low index of refraction (n<1.5); selecting and reacting zero,one, or more monomers having a high index of refraction (n≧1.5), whereinthe concentration of the monomer(s) with a high index of refraction isless than the concentration of monomer(s) having a low index ofrefraction; selecting and reacting zero, one or more optically activechromophores according to the invention, or zero, one, or more ofconventional optical chromophores disclosed herein, with the provisothat at least one chromophore must be selected; selecting and reacting acompatibilizer according to the invention for the selectedchromophore(s); and selecting and reacting one or more adhesionenhancers according to the invention. Typically, to obtain propertiessuch as high T_(g) while obtaining good optical properties, fluorinatedmonomers are mixed with nonfluorinated monomers. Additional materials toobtain selected properties such as electrical properties, flow control,water resistance and the like may be added.

[0030] B. For a high refractive index optical system (e.g. non-silicabased optical waveguide systems): selecting and reacting one or moremonomers having a high index of refraction (n≧1.5) according to theinvention; selecting and reacting zero, one, or more monomers having alow index of refraction (n<1.5) according to the invention (wherein theconcentration of the monomer having a low index refraction is less thanthe monomer having a high index of refraction), selecting and reactingzero, one or more optically active conventional chromophores disclosedherein, or zero, one, or more of the optically active chromophoresaccording to the invention; selecting and reacting one or morecompatibilizers for the one or more chromophores; and selecting andreacting one or more adhesion enhancers according to the invention.Typically, to obtain properties such as high T_(g) while maintaininggood optical properties, fluorinated monomers are mixed withnonfluorinated monomers. Additional materials to obtain selectedproperties such as electrical properties, flow control, waterresistance, and the like may be added.

[0031] The typical polymer systems or functional optical materials ofthe present invention are derived from selected combinations of thefollowing materials:

[0032] (i) low refractive index monomers; p0 (ii) high refractive indexmonomers;

[0033] (iii) polar and nonpolar monomers;

[0034] (iv) optically active chromophores such as EO chromophores(conventional and those from this invention) that react with monomers ofthis invention or blend with the polymers of this invention;

[0035] (v) monomers that act as compatibilizers or solubilizers foroptically active chromophores such as EO or thermooptic chromophoresthat are blended with the materials of this invention;

[0036] (vi) monomers that act as compatibilizers or solubilizers foroptically active chromophores such as EO or thermooptic chromophoresthat react with monomers for forming polymers according to theinvention;

[0037] (vii) adhesion promotion monomers (e.g., for glass and metalelectrodes),

[0038] (viii) monomers that provide thermal stability

[0039] (ix) monomers that provide moisture resistance;

[0040] (x) monomers which increase or provide high Tg values (e.g.,greater than 100° C.);

[0041] (xi) monomers capable of providing thermoplastic andthermosetting polymer structures;

[0042] (xii) monomers that allow for enhanced poling; and

[0043] (xiii) monomers that provide enhanced flow characteristics duringformation of the final product.

[0044] The various examples provide herein include the methodologynecessary to synthesize polymer systems which possess the durability andefficiency required for commercial optical systems such as opticalswitches, optical modulators, and other optical components that may beused in conjunction with silica or non-silica waveguides. As isdescribed in more elsewhere herein, monomers and precursors that providea low refractive index are preferred for silica based devices andmonomers and precursors that provide a high refractive index aretypically preferred for non-silica based devices. Silica based systemstypically require a polymer system or polymer composition that has arefractive index of about 1.3 to about 1.5. Typically monomers and thequantity of the respective monomer are selected that will providerefractive indexes within this range in the final functional opticalmaterial. Typically for use with silica based optical systems and withoptical systems that behave similarly to silica systems, monomers areselected from the group of monomers that produce homopolymers having arefractive index below 1.5. However, this may not always be the case asit is envisioned that small quantities of monomer from homopolymershaving refractive indexes above about 1.5 may be incorporated ascomonomers with the low refractive index (n<1.5) producing monomers toachieve specific effects in the final functional optical material (e.g.higher T_(g), optically active chromophore compatibilization, shiftedoptical loss at specific wavelengths, better poling, adhesion, enhancedcrosslinking, and the like). However, in silica based systems andsystems having like properties, the majority of the monomer content willalways be a majority of one or more monomers having low refractiveindexes. Typically for use with non-silica based optical systems,monomers are selected from the group of monomers that producehomopolymers having a refractive index above about 1.5. However, thismay not always be the case as it is envisioned that small quantities ofmonomer from homopolymers having refractive indexes below 1.5 may beincorporated as comonomers with the high refractive index producingmonomers (n≧1.5) to achieve specific effects in the final functionaloptical material (e.g. higher T_(g), optically active chromophorecompatibilization, shifted optical loss at specific wavelengths, betterpoling, adhesion, enhanced crosslinking and the like). This methodologyincludes the combination of acrylic, methacrylic, styrene and otherliquid or solid ethylenically unsaturated monomers.

[0045] Typically the optically active chromophores of the presentinvention, including fluorinated chromophores and those having primaryas well as secondary electron withdrawing groups, are used with silicabased optical systems. In some cases, the conventional chromophores maybe used with low refractive index systems such as silica. Typically, theconventional EO chromophores as well as the chromophores of the presentinvention, may be used with non-silica based optical systems.Compatibilizers useful with EO chromophores of the present inventiontypically include nitrites, fluorinated esters, and fluorinatedaromatics. Compatibilizers useful with conventional EO chromophorestypically include nitrites, esters, and aromatics.

[0046] Electrooptic measurement techniques used in the present inventionare described in Electro-optic coefficient determination in StratifiedOrganized Molecular Thin Films. Application to Poled Polymers, P. A.Chollet, et al; Thin Solid Films 242 (1994), 132-138; and SimpleReflection Techniques for Measuring the Electro-optic Coefficient ofPoled Polymers, C. C. Teng and H. T. Man, Appl. Phys. Lett., Vol. 56.No. 18, (1990), 1734-1736.

[0047] The preferred polymers of the present invention can be preparedaccording to methods found in Preparative Methods of Polymer Chemistry,Sorenson and Campbell, Interscience Publishers, New York, N.Y. (1968),and include linear polymers, lightly branched linear polymers, andheavily branched linear polymers. The preferred thermoplastic polymersof the present invention include: acrylics/methacrylics (copolymers ofesters of acrylic and methacrylic acid where the alcohol portion of theester can be based on hydrocarbon or partially or fully fluorinatedalkyl chains); polyesters (where the diacid or diol can containcarbon-hydrogen aliphatic, aromatic or carbon-fluorine functionality);polyurethanes (where the diisocyanate can be aliphatic or aromatic andthe diol can contain carbon-hydrogen or carbon-fluorine functionality);polyimides where the acid, amine, or diamine can be partially or fullyfluorinated; polyamides (where the diacid or diamine can containcarbon-hydrogen aliphatic, aromatic or carbon-fluorine functionality);polyphosphazenes (where the polyphosphazene backbone structure cancontain fluorinated aromatic or aliphatic functional groups, as well as,carbon-hydrogen functionality); epoxy resin (where the epoxy resin cancontain carbon-hydrogen or carbon-fluorine functionality) which canfurther be reacted with diacids or anhydrides (that also containcarbon-hydrogen or carbon-fluorine functionality); and hybrid(organic-inorganic) or nanocomposite polyester polymers (where thepolyester component consists of aliphatic, aromatic carbon hydrogen orcarbon-fluorine functionality and the inorganic components are based onsilane or organometallic materials such as titanates, zirconates andother multivalent metal organics). The general chemical structures ofthese preferred polymers is as follows:

[0048] Acrylic (polymers of acrylic acid ester monomers)

[0049] Copolymers of acrylic acid esters, methacrylic acid esters andother single unsaturated monomers

[0050] In Tables 1, 2 and 3 are listed a number of monomer systems thathave low refractive index (n) values (n=about 1.33 to about 1.50) andhigh refractive index values (n=greater than about 1.50, preferablygreater than about 1.50 to about 1.6. TABLE 1 Acrylate MonomersRefractive index Name (at 20° C.) Acid 1.4202 Allyl ester 1.4320Anhydride 1.4487 Benzyl ester 1.5143 4-Biphenylyl ester Bisphenol Aethoxylate diester 1.5450 Bisphenol A diglycidyl ether diester 1.55702-Bromo- 3-Bromo-, cis- 2-Bromo-, ethyl ester 2-Bromoethyl ester 1.47702-Bromomethyl- 2-Bromomethyl-, ethyl ester 1.478 2-Bromomethyl-, methylester 1.490 1,3-Butylene diester 1.4500 1,4-Butylene diester 1.45602-Butylene-l,4 diester 1.4422 2-(2-Butoxyethoxy)ethyl ester 1.43942-Butoxyethyl ester 1.4323 n-Butyl ester 1.4180 s-Butyl ester 1.4140t-Butyl ester 1.4108 2-Chloro- 2-Chloro-, butyl ester 2-Chloro-, ethylester 1.4384 2-Choloro-, methyl ester 1.4420 3-Chloro-, cis- 3-Chloro-,trans- 2-Chloroethyl ester 1.4384 Cinnamyl ester 1.5660 Crotyl ester2-Cyano-, butyl ester 1.4420 2-Cyano-, ethyl ester 2-Cyano-, isobutylester 2-Cyanoethyl ester 1.4433 Cyclohexyl ester 1.4673 Cyclopentylester n-Decyl ester 1.440 2,3-Dibromopropyl ester 1.55202,3-Dichloropropyl ester 1.4765 Dicyclopentenyl esterDicyclopentenyloxyethyl ester 1.5010 2-(Diethylamino)ethyl ester 1.4433-(Diethylamino)propyl ester 1.441 Di(ethylene glycol) diester 1.4630Dihydrodicyclopentadienyl ester 1.509 2,3-Dihydroxypropyl ester2(Dimethylamino) ethyl ester 1.4380 3-(Dimethylamino) neopentyl ester1.439 3-(Dimethylamino) propyl ester 1.4400 Dipentaerythritol pentaesterDi(propylene glycol) diester 1.4488 Di(trimethylolpropane) tetraester1.4790 Dodecyl ester 1.4450 1H,1H,11H-Eicosafluoroundecylester2-(2-Ethoxyethoxy)ethyl ester 1.4390 2-Ethoxyethyl ester 1.4282 Ethylester 1.4060 Ethylene diester 1.4610 2-Ethylhexyl ester 1.4360 Furfurylester 1.4800 Glycidyl ester 1.4490 Glycerol propoxylate triester 1.46101H,1H,2H,2H-Heptadecafluorodecyl ester 1.3380 1H,1H-Heptafluorobutylester 1.3301 Heptyl ester 1.4311 Hexadecyl ester 1.44702,2,3,4,4,4-Hexafluorobutyl ester 1.352 1H-Hexafluoroisoporpyl ester1.3190 Hexanediol diester 1.4562 n-Hexyl ester 1.4280 4-Hydroxybutylester 1.4520 2-Hydroxyethyl ester 1.4502 2-Hydroxy-3-phenoxypropyl ester1.5280 2-Hydroxypropyl ester 1.4448 Isobornyl ester 1.4760 Isobutylester 1.4140 Isodecyl ester 1.4420 Isooctyl ester 1.4370 Isopropoxyethylester 1.4258 Isopropyl ester 1.4060 Methallyl ester 1.43722-(2-Methoxyethoxy) ethyl ester 1.4392 2-Methoxyethyl ester 1.4272Methyl ester 1.4020 2-Methylbutyl ester 1.4800 2-(N-Morpholino)ethylester 1.4728 1-Naphthyl ester 2-Naphthyl ester Neopentyl ester Neopentylglycol diester 1.4530 Nonyl ester 1.4375 Octadecyl ester1H,1H,5H-Octafluoropentyl ester 1.3467 n-Octyl ester 1.43501H,1H-Pentadecafluorooctyl ester 1.3279 Pentaerythritol tetraester1.4870 Pentaerythritol triester 1.4840 Pentaerythritol stearate diester2,2,3,3,3-Pentafluoropropyl ester 1.3363 1,5-Pentanediol diester 1.4551n-Pentyl ester 1.4240 2-Phenoxyethyl ester 1.5180 Phenyl ester1,4-Phenylene diester 1,4-Phenylene di(acrylic acid) 2-Phenylethyl esterTrimethyl 2-phosphonoacrylate 1.4540 Propargyl ester n-Propyl ester1.4130 1,2-Propylene glycol diester 1.4470 1,3-Propylene glycol diester1.4529 Tetradecyl ester 1.4468 Tetra(ethylene glycol) diester 1.46382,2,3,3-Tetrafluoropropyl ester 1.3629 Tetrahydrofurfuryl ester 1.4580S,S′-Thiodi-1,4-phenylene dithiol diester 2,3,3-Trichloro- Tridecylester Tri(ethylene glycol) diester 1.4609 2,2,2-Trifluoroethyl ester1.3506 1,1,1-Tri(2-hydroxyethoxy-methyl)propane 1.4710 triesterTri(2-hydroxyethyl) isocyanurate triester 3,5,5-Trimethylcyclohexylester 1.455 3,5,5-Trimethylhexyl ester 1.4370 Trimethylolpropanetriester 1.4736 Trimethylolpropane ethoxylate triester 1.4720Tri(propylene glycol) diester 1.4500 Vinyl ester 1.4320

[0051] TABLE 2 Methacrylate Monomers Refractive index Name (at 20° C.)Acid 1.432 2-(Acetonacetoxy)ethyl ester 1.4560 Allyl ester 1.4360Anhydride 1.454 2-(1-Aziridinyl)ethyl ester Benzyl ester 1.5120Bisphenol A diester Bisphenol A tetraethozylate diester 1.53202-Bromoethyl ester 1,3-Butylene diester 1.4520 1,4-Butylene diester1.4565 2-Butoxyethyl ester 1.4335 n-Butyl ester 1.4230 s-Butyl ester1.4195 Tert-Butyl ester 1.4150 N-tert-Butyl-2-aminoethyl ester 1.44202-Chloro-2-hydroxypropyl ester 1.4750 2-Chloroethyl ester Chloromethylester 1.4434 Cinnamyl ester Chloride 1.4420 2-Cyanoethyl ester 1.44591,4-Cyclohexanediol diester Cyclohexyl ester 1.459 Decanediol diester1.4577 Decyl ester 1.443 2,3-Dibromopropyl ester 2-(Dibutylamino)ethylester 1.4474 Dicyclopentenyl ester 1.4990 Dicyclopentenyloxyethyl ester1.4970 2-(Diethylamino) ethyl ester 1.4442 3-(Dimethylamino) propylester Di(Ethylene glycol) diester 1.4580 3,4-Dihydroxybutyl ester2,3-Dihydroxypropyl ester 2-(Dimethylamino) ethyl ester 1.4400Diurethane diester (isomers) 1.485 1H,1H,7H-Dodecafluoroheptyl esterDodecanediol diester Dodecyl ester 1.4450 2,3-Epithiopropyl ester2,3-Epoxybutyl ester 1.4422 3,4-Epoxybutyl ester 1.4472 2,3-Epolyopropylester 1.4490 4-Ethoxybutyl ester 1.4223 2-Ethoxyethyl ester 1.4290 Ethylester 1.4130 Ethyl 2-bromomethyl- ester 1.4790 2-Ethylbutyl ester1,2-Ethylene diester 1.4540 2-Ethylhexyl ester 1.4380 2-(Ethylthio)ethylester Ethyl 2-(trimethoxysilylmethyl-) ester 1.4380 Furfuryl ester1.4820 Glycerol diester 1.4720 Glycerol triester Glycidyl ester 1.44901H,1H,2H,2H-Heptadeca-fluorodecyl ester 1H,1H-Heptafluorobutyl ester1.3410 Heptyl ester 1,6-Hexanediol diester 1.45802,2,3,4,4,4,-Hexafluorobutyl ester 1.3610 1H-Hexafluoroisopropyl ester1.3310 Hexyl ester 1.432 4-Hydroxybutyl ester 2-Hydroxyethyl ester1.4520 3-(5-Hydroxypentyloxy)-3- oxopropyl ester 3-Hydroxyporopyl ester1.4470 Isobornyl ester 1.4770 Isobutyl ester 1.420 2-Isocyanatoethylester Isodecyl ester 1.4430 Isopropyl ester 1.4122 Metallyl ester2-(2-Methoxyethoxy) ethyl ester 1.4397 2-Methoxyethyl ester 1.4310Methyl ester 1.4140 2-Methyl-2-nitropropyl ester 1.450 2-(Methylthio)ethyl ester 1.4800 Methyl 2-bromomethyl ester 1.4900 Methyl2-(1-hydroxyethyl-)ester 1.4520 2-N-Morpholinoethyl esterNeopentylglycol diester 1.4530 Nona(ethylene glycol) diester 1.4660Nona(propylene glycol)diester 1.4520 Nonyl ester 1.4660 4-Nonylphenylester 1.5020 n-Octyl ester 1.4373 Pentabromophenyl esterPentachlorophenyl ester 1H,1H-Pentafluorooctyl ester Pentaerythritoltetraester 2,2,3,3,3-Pentafloropropyl ester 1.3482 Pentyl ester2-Phenoxyethyl ester 1.5130 Phenyl ester 1.5184 2-Phenylethyl ester1.508 n-Propyl ester 1.4450 1,2-Propylene diester 1.4450 1,3-Propylenediester 2-Sulfoethyl ester 1.4772 3-Sulfopropyl ester, potassium saltTetra(ethylene glycol) diester 1.4630 2,2,3,3-Tetrafluoropropyl ester1.3730 Trimethylsilyl ester 1.4147 2-(Trimethylsilyloxy)ethyl ester1.4280 3-(trimethylsilyloxy)propyl ester 1.43103-(Tris(trimethylsilyloxy)silyl) propyl ester 1.4190 Vinyl ester 1.4360

[0052] TABLE 3 Other Ethylenically Unsaturated Liquid or Solid MonomersMonomers Refractive Index (at 20° C.) Styrene 1.5470 α, βDifluorostyrene 1.506 1, 2 Difluorostyrene 1.4990 2, 6 Difluorostyrene1.4990 Monofluorostyrene 1.51 Trifluoromethylstyrene 1.46-1.47Pentafluorostyrene 1.446 Vinyl acetate 1.3950 Vinyl trifluroethylacetate1.3170 Vinyl ethers 1.37-1.52 Vinyl amides 1.48-1.51 Vinyl esters1.31-1.55 Butenes and butadiene 1.37-1.57 Maleate/fumarate esters 1.4-1.49 Acrolein 1.4025 Acryl and methacrylamides 1.41-1.51 Allylmonomers 1.38-1.56

[0053] The following table, Table 4, lists limits typical of thecompositions and polymers described in Tables 5, 6, and 13. TABLE 4Critical Limits for Polymers Polymer low refractive index range 1.3 < n< 1.5 Polymer high refractive index range 1.5 ≦ n < 1.8 Water MoistureSensitivity less than 2% water absorption by the polymer in a 24 hourwater immersion test at room temperature. Ease of poling less than 100volts per micron of film thickness Thermal stability less than 10%weight loss at 200° C. Adhesion better than about 90% crosshatchadhesion to any given substrate (ASTM D3359- 78) Optical Clarity lessthan 5% by weight hydrogen in the monomer repeat unit of the polymer,and other units of the polymer. EO Chromophore compatability less than1% weight loss or phase separation of the EO chromophore in the polymermatrix.

POLYMER EXAMPLE 1 Prior Art Polymer

[0054] The exact co-polymer system 1H, 1H, 2H, 2HTridecafluoro-octylmethacrylate (48.5%), trifluoroethylmethacrylate(19.4%)(monomer, n=1.361), methacrylic acid ester of Disperse Red-1(32.1%) (conventional chromophore) described in Bosc et al. was preparedand tested for its potential of creating a practical commercialcommunications optical switch device. The test results for this priorart system are given in Table 5. Descriptions of the results in each ofthe testing criteria follow Table 5. TABLE 5 Analysis of Prior ArtTerpolymer Control Thermal of Total stability/ Water/ Ease EO SystemRefrac- Opti- {cross- Moisture of (conventional) Refrac- tive callinking Sensit- Pol- Adhe- Chromophore tive Index Tg loss capability}ivity ing sion Compatibility Index Low Less Poor Poor/ Poor Poor PoorPoor Poor (n = 1.5) than {none} 100° C. (373° K)

[0055] Regarding optical loss, the electrooptic (EO) chromophore andmonomer has a high percentage of carbon-hydrogen bonds, which can causehigh optical losses at 1.3 um wavelengths of light (communicationrequirements).

[0056] Regarding thermal stability, the low Tg for this copolymer system(84° C.) allows the material to melt on flow above 100-130° C. Thissystem is not crosslinked and is thermoplastic in its nature and thuscan melt/flow at high temperatures. The low thermal stability of thispolymer also limits the ability of the polymer to maintain its polingcapabilities over a long time period.

[0057] Regarding moisture sensitivity, copolymer films containing goldelectrodes and on quartz or ITO coated quartz substrates were easilyremoved or debonded either by water immersion or subjection to 85%RH/85° C. environmental exposure conditions.

[0058] Regarding ease of poling, this copolymer had a tendency tobreakdown (form pinholes) and short out the electrodes under a widerange of DC voltage poling conditions.

[0059] Regarding adhesion, this copolymer could be easily removed fromquartz substrates using a scratch or cut/tape adhesion test.

[0060] Regarding EO chromophore compatibility, a common electrooptic(EO) chromophore such as Disperse Red 1 is not soluble or compatible inthe copolymer compositions disclosed in the prior art. Copolymerizationof all carbon-hydrogen monomer of Disperse Red 1 does allow one to putin a small amount (less than 50%) of the EO chromophore but overtime/temperature this copolymerized EO chromophores can segregate awayfrom the copolymer and lower its EO efficiency and optical clarity(increased optical loss).

[0061] Regarding control of total system refractive index, theconventional electrooptic (EO) chromophore has a very high inherentrefractive index value. For this reason higher concentrations of the EOchromophore raises the entire refractive index value of the total systemto where it is no longer efficient for optical switching in a silicawaveguide or other applications requiring low refractive index values.In order to reduce the overall refractive index of the system one needsto use a lower concentration of the conventional EO chromophore, whichreduces the overall switching capability or efficiency of the entiresystem.

[0062] The development of a practical and robust (durable) polymersystem for silica waveguide optical switch communications componentsrequires the following elements:

[0063] (a) control of the overall refractive index of the total system(n<1.5);

[0064] (b) control of the Tg and crosslinking capability of the totalsystem;

[0065] (c) control of the optically active chromophore compatibility andlow optical loss (low numbers of C—H bonds) of the system;

[0066] (d) inherent water resistance and strong adhesive bondingcapabilities for silica and metal (gold, silver, aluminum, nickel, etc.)electrode substrates; and

[0067] (e) a total system designed for enhanced poling capabilities,high dielectric strength and breakdown resistant capabilities.

[0068] The first step in this embodiment of the present invention is theselection of low or refractive index monomers as exemplified in Tables1, 2, and 3 (refractive index adjustment or control), and in Table 8where the monomer of a homopolymer having appropriate properties can beselected. The monomers, and monomers of homopolymers listed in thesetables are meant to be exemplary and are not to be construed as alimitation on the invention. Other monomers, not listed in the tablesthat possess the properties required by the present invention may alsobe used. When monomers are mixed, the refractive index of themulti-component polymer is controlled by altering the fractional amountof each monomer contained in the polymer. The refractive index of themulti-component polymer can be made to vary smoothly between the lowestrefractive index of a homopolymer formed from any one component and thehighest refractive index of a homopolymer formed from any othercomponent.

POLYMER EXAMPLE 2 Novel Thermoplastic Polymer

[0069] As an example for this embodiment, a low refractive index monomerselected was trifluoroethylmethacrylate (n=1.361). The next monomersselected (acrylonitrile, methylmethacrylate, {pentafluorostyrene inPolymer Example 3}) were used to compatabilize a conventional (allcarbon hydrogen bonds) EO chromophore (meta-nitroaniline or DisperseRed-1) and to raise the Tg of the total system. The next monomerselected was methacryloxypropyltrimethoxysilane which can promoteadhesion to silica or Indium tin oxide coatings.

[0070] The multi-monomer thermoplastic polymer of this invention wasprepared in the following manner (all in wt. %):

[0071] 60% of trifluoroethylmethacrylate monomer (n=1.361) was combinedwith 30% methylmethacrylate monomer (n=1.49),

[0072] 8% acrylonitrile (compatibility promoter for the chromophore) and2% of the methacryloxypropyltrimethoxysilane (adhesion promoter). Thisliquid monomer mixture (25 cc) was added slowly to 200 mls of drytetrahydrofuran (THF) contained in a 400 ml round bottom 3 neck flashfitted with a heating mantle, glass shaft stirrer, reflux condenser andaddition funnel. To the monomer mixture was added 0.5 grams of Vazo 64™(free radical initiator from E. I. DuPont DeNemours, Wilmington, Del.,USA) and the entire mixture heated in the THF at 68° C. over a 1 hourtime period. The reaction was continued over an 8 hour time period afterwhich the THF/polymer solution was cooled to room temperature and thepolymer precipitated out of the solution with excess methanol. Theresulting polymer had a refractive index value below 1.5 and a Tg valuegreater than 100° C.

[0073] To this polymer was added 10% by weight of a conventional EOchromophore (metanitroaniline or Disperse Red-1) or an EO chromophore ofthis invention (4-fluoro-3-nitroaniline)in dioxane (1-5% solids) andspun down onto Indium Tin Oxide (ITO) coated glass or silica substrates.This system was metalized and poled in a similar manner as PolymerExample 1. See, for example, Electro-optic coefficient determination inStratified Organized Molecular Thin Films: Application to poledpolymers, P. A. Chol let, et al; Thin Solid Films 242: 132-138 (1994);and, Simple reflection techniques for measuring the electro-opticcoefficient of poled polymers, C. C. Teng and H. T. Man, Appl. Phys.Lett., Vol. 56 No. 18: 1734-1736 (1990).

[0074] The poling and dielectric strength capabilities for thisparticular copolymer was superior (less pinholes, defects and electricalshorting) to the prior art example discussed previously. This copolymerwas analyzed in the same fashion as the prior art polymer in PolymerExample 1. The data from this analysis is given in Table 6. TABLE 6Novel Thermoplastic Polymer (Polymer Example 2) EO (conventionalChromophore Control Thermal compatibility) of Total Stability Water/{Non Conven- Sytem Refrac- Opti- {cross- moisture tional EO Refract-tive cal linking Sensit- Ease of Adhe- Chromophore ive Index Tg Losscapability} ivity Poling sion compatability} Index Low 100 Lowacceptable Good Good Excel- Good good n < 1.5 ° C.> {none} lent{excellent}

[0075] This novel polymer had a Tg>100° C. and thus was not assusceptible to thermal stress as the prior art polymer system. Theaddition of crosslinking capability greatly improved the overall thermalstability of the system. Additionally, this polymer has excellent waterresistance and excellent adhesion to silica surfaces, indium tin oxidecoatings and gold electrodes. Both the nitrile and silane functionalgroups in the polymer are responsible for adhesion.

[0076] The nitrile functional group in the polymer and the hydrocarbonester increased the solubility (up to 10%) of the conventional EOchromophore but the fluorine containing EO chromophores of thisinvention could be put into this polymer up to a 30% or greater loadingwhile still maintaining the overall is low refractive index for thetotal system.

POLYMER EXAMPLE 3 Novel Thermoplastic Polymers

[0077] Another embodiment of this invention includes, a copolymer systemprepared in a manner similar that in Polymer Example 2, but here themethylmethacrylate monomer was replaced with pentafluorostyrene monomer(n=1.446). This particular system had even greater water resistance andadhesion than Polymer Example 2, while still maintaining EO responsecapabilities with conventional EO chromophores, or EO chromophores ofthe present invention.

[0078] A number of other homopolymer and copolymers were prepared in asimilar manner as the previous examples and their compositions andgeneral properties summarized in Table 7. TABLE 7 Thermoplastic PolymersUseful with this Invention Concen- General Sample tration PropertyNumber Monomers (gm) Product Comments 1 Trifluoroethyl 25 HomopolymerLow n, low Acrylate Tg 2 Trifluoroethyl- 17 Copolymer Low n, goodmethacrylate adhesion Acrylonitrile 5 3 Trifluoroethyl- 8 Copolymer Lown, poor methacrylate adhesion Methylmethacrylate 5 4 Trifluoroethyl- 11Copolymer n = Approx. methacrylate 1.5, good Methylmethacrylate 11adhesion Acrylonitrile 2.5 and good Trimethoxysilylpropyl- 0.5 watermethacrylate resistance 5,7* Trifluoroethyl- 4 Copolymer n = <1.49,methacrylate high water Methylmethacrylate 10 sensitivity 6Trifluoroethyl- 9 Homopolymer Low n, poor methacrylate adhesion

[0079] Table 8 provides a list of homopolymer systems compatible withthe methodology of the present invention (see Polymer Example 3). Thesehomopolymer systems have low n values (about 1.3 to <1.50); and high nvalues (n≧1.5). Additionally, Table 8, lists glass transition (Tg)values (° K) for these homopolymers, as well as providing commentsregarding a given homopolymer's polarity, adhesion bonding capabilitiesand water sensitivity. TABLE 8 HomoPolymer System Properties GlassTransition Refractive Temperature Polymer Index (n) (Tg) (° K) CommentsPoly(pentadecafluorooctyl acrylate) 1.339 256Poly(tetrafluoro-3-(heptafluoropropoxy)propyl 1.346 acrylatePoly(tetrafluoro-3-(pentafluoroethyoxy)propyl 1.348 acrylate)Poly(undecafluorohexyl acrylate) 1.356 234 Poly(nonafluoropentylacrylate) 1.360 Poly(tetrafluoro-3-(trifluoromethyoxy)propyl 1.360acrylate) Poly(pentafluorovinyl propionate) 1.364 Poly(heptafluorobutylacrylate) 1.367 330 Poly(trifluorovinyl acetate) 1.375Poly(octafluoropentyl acrylate) 1.380 238 Poly(pentafluoropropylacrylate 1.385 Poly(2-heptafluorobutoxy)ethyl acrylate) 1.390Poly(2,2,3,4,4,4-hexafluorobutyl acrylate) 1.392 251 Poly(trifluoroethylacrylate) 1.407 263 Poly(2-(1,1,2,2-tetrafluoroethyoxy)ethyl acrylate1.412 Poly(trifluoroisopropyl methacrylate) 1.4177 354Poly(2-trifluoroethyoxy)ethyl acrylate 1.4185 Poly(trifluoroethylmethacrylate) 1.437 Poly(vinyl-isobutyl ether) 1.4507 Poly(vinyl ethylether) 1.4540 Poly(vinyl butyl ether) 1.4563 Poly(vinyl pentyl ether)1.4581 Poly(vinyl hexyl ether) 1.4591Poly(4-fluoro-2-trifluoromethylstyrene) 1.46 Poly(vinyl octyl ether)1.4613 Poly(vinyl-2-ethylhexyl ether) 1.4626 Poly(vinyl decyl ether)1.4628 Poly(2-methoxyethyl acrylate) 1.463 Poly(butyl acrylate) 1.4631219 1.466 Poly(tert-butyl methacrylate) 1.4638 391 Poly(vinyl dodecylether) 1.4640 Poly(3-ethoxypropyl acrylate) 1.465 Poly(vinyl propionate)1.4665 Poly(vinyl acetate) 1.4665 a, c Poly(vinyl methyl ether) 1.467 a,c Poly(ethyl acrylate) 1.4685 Poly(vinyl methyl ether) (isotactic)1.47-1.48 a, c Poly(3-methoxypropyl acrylate) 1.4700 Poly(2-ethoxyethylacrylate 1.471 a, c Poly(methyl acrylate) 1.471 283 Poly(isopropylmethacrylate) 1.472-1.480 354 Poly(vinyl sec-butyl ether) (isotactic)1.4740 Poly(dodecyl methacrylate) 1.4740 208 Poly(tetradecylmethacrylate) 1.4746 201 Poly(hexadecyl methacrylate) 1.4750 288Poly(vinyl formate) 1.4757 Poly(2-fluoroethyl methacrylate) 1.4768Poly(isobutyl methacrylate) 1.477 326 Poly(n-hexyl methacrylate) 1.4813268 Poly(n-butyl methacrylate) 1.483 293 Poly(ethylene dimethacrylate)1.4831 Poly(2-ethoxyethyl methacrylate) 1.4833Poly(oxyethyleneoxymaleoyl)(poly(ethylene 1.4840 maleate) Poly(n-propylmethacrylate) 1.484 308 Poly(3,3,5-trimethylcyclohexyl methacrylate)1.485 Poly(ethyl methacrylate) 1.485 338 Poly(2-nitro-2-methylpropylmethacrylate) 1.4868 Poly(triethylcarbinyl methacrylate) 1.4889Poly(1,1-diethypropyl methacrylate) 1.4889 Poly(methyl methacrylate)1.4893 373 Poly(ethyl glycolate methacrylate) 1.4903Poly(3-methylcyclohexyl methacrylate) 1.4947 Poly(cyclohexyl

-ethoxyacrylate) 1.4969 Poly(4-methylcyclohexyl methacrylate) 1.4975Poly(decamethylene glycol dimethacrylate) 1.4990 bPoly(2-bromo-4-trifluoromethylstyrene) 1.5 Poly(sec-butyl

-chloroacrylate) 1.500 Poly(ethyl

-chloroacrylate) 1.502 Poly(2-methylcyclohexyl methacrylate) 1.5028Poly(bornyl methacrylate) 1.5059 Poly(ethylene glycol dimethacrylate)1.5063 b Poly(cyclohexyl methacrylate) 1.5066 377 Poly(cyclohexanediol-1,4-dimethyacrylate) 1.5067 b Poly(tetrahydrofurfuryl methacrylate)1.5096 Poly(1-methylcyclohexyl methacrylate) 1.5111 Poly(2-hydroxyethylmethacrylate) 1.5119 358 a, b, c Poly(vinyl chloroacetate) 1.512Poly(vinyl methacrylate) 1.5129 Poly(N-butyl methacrylamide) 1.5135Poly(methyl

-chloroacrylate) 1.517 Poly(2-chloroethyl methacrylate) 1.517Poly(2-diethylaminoethyl methacrylate) 1.5174 a, cPoly(2-chlorocyclohexyl methacrylate) 1.5179 Poly (allyl methacrylate)1.5196 b Poly(methyl isopropenyl ketone) 1.5200 Poly(ester) resin, rigid(ca. 50% styrene) 1.523-1.54 b Poly(N-2-methoxyethyl) methacrylamide)1.5246 Poly(acrylic acid) 1.527 379 a, b, c Poly(1,3-dichloropropylmethacrylate) 1.5270 Poly(2-chloro-1-(chloromethyl)ethyl 1.5270methacrylate) Poly(acrolein) 1.529 Poly(1-vinyl-2-pyrrolidone) 1.53 a, cPoly(cyclohexyl

-chloroacrylate) 1.532 Poly(2-chloroethyl

-chloroacrylate) 1.533 Poly(2-aminoethyl methacrylate) 1.537 a, cPoly(furfuryl methacrylate) 1.5381 Poly(butylmercaptyl methacrylate)1.5390 Poly(1-phenyl-n-amyl methacrylate) 1.5396Poly(N-methyl-methacrylamide) 1.5398 Poly(sec-butyl

-bromoacrylate) 1.542 Poly(cyclohexyl

-bromoacrylate) 1.542 Poly(2-bromoethyl methacrylate) 1.5426Poly(ethylmercaptyl methacrylate) 1.547 Poly(N-allyl methacrylamide)1.5476 b Poly(1-phenylethyl methacrylate) 1.5487 Poly(vinylfuran) 1.55Poly(2-vinyltetrahydrofuran) 1.55 a, c Poly(p-methyoxybenzylmethacrylate) 1.552 Poly(isopropyl methacrylate) 1.552Poly(p-isopropylstyrene) 1.554 Poly(p,p-xylylenyl dimethacrylate) 1.5559b Poly(1-phenylallyl methacrylate) 1.5573 b Poly(p-cylcohexylphenylmethacrylate) 1.5575 Poly(2-phenylethyl methacrylate) 1.5592Poly(1-(0-chlorophenyl)ethyl methacrylate 1.5624 Poly(styrene-co-maleicanhydride) 1.564 b, c Poly(1-phenylcyclohexyl methacrylate) 1.5645Poly(methyl

-bromoacrylate) 1.5672 Poly(benzyl methacrylate) 1.5680Poly(2-phenylsulfonyl)ethyl methacrylate) 1.5682 Poly(m-cresylmethacrylate) 1.5683 Poly(o-methoxyphenyl methacrylate) 1.5705Poly(phenyl methacrylate) 1.5706 407 Poly(o-cresyl methacrylate) 1.5707Poly(diallyl phthalate) 1.572 b Poly(2,3-dibromopropyl methacrylate)1.5739 Poly(vinyl benzoate) 1.5775 Poly(1,2-diphenylethyl methacrylate)1.5816 Poly(o-chlorobenzyl methacrylate) 1.5823 Poly(m-nitrobenzylmethacrylate) 1.5845 Poly(N-(2-phenylethyl)methacrylamide) 1.5857Poly(4-methoxy-2-methylstyrene) 1.5868 Poly(o-methylstyrene) 1.5874Poly(styrene) 1.59-1.592 Poly(o-methoxystyrene) 1.5964 348Poly(diphenylmethyl methacrylate) 1.5933 Poly(p-bromophenylmethacrylate) 1.5964 Poly(N-benzyl methacrylamide) 1.5965Poly(p-methoxystyrene) 1.5967 Poly(o-chlorodiphenylmethyl methacrylate)1.6040 Poly(pentachlorophenyl methacrylate) 1.608 Poly(0-chlorostyrene)1.6098 Poly(phenyl

-bromoacrylate) 1.612 Poly(p-divinylbenzene) 1.6150 bPoly(N-vinylphthalimide) 1.6200 Poly(2,6-dichlorostyrene) 1.6248 440Poly(β-naphthyl methacrylate) 1.6298 Poly(

-naphthyl carbinyl methacrylate 1.63 Poly(2-vinylthiophene) 1.6376 Poly(

-naphthyl methacrylate) 1.6410 Poly(vinyl phenyl sulfide) 1.6568Poly(vinylnaphthalene) 1.6818 Poly(vinylcarbazole) 1.683Poly(pentabromophenyl-methacrylate) 1.71

[0080] Table 9 shows how different polymer systems and blends interactwith conventional EO chromophores and the EO chromophores of the presentinvention, and influence the refractive index of the total system. TABLE9 Thermoplastic Polymer Combinations (Conventional EO Chromophores andEO Chromophores of the Present Invention Refrac- Film tive Thick- Smpl.Index ness No. Polymer System EO Chromophore (n) (um) 1 50/50 blend ofNone 1.465 — polymethyl- methacrylate and trifluoroethyl- methacrylate/acrylonitrile copolymer (sample 2, Table 7) 2 (1 gram sample) 0.01 gmDisperse Red- 1.51 0.49 (Sample 2, Table 7) 1 (conventional EOchromophore) 3 1 gram sample 0.01 gm Disperse Red- 1.51 1.0 (Sample 2,Table 7) 1 (conventional EO chromophore) 4 1 gram sample 0.01 gmDisperse Red- 1.51 1.24 polymethyl- 1 (conventional EO methacrylatechromophore) 5 1 gram sample Neither Disperse Red-1 — — (Sample 6, Table7) nor nitroaniline were (homopolymer of soluble in this polymertrifluoroethyl- (conventional EO methacrylate) chromophores) 6 1 gramsample 0.01 gm fluorinated 1.49 0.49 (Sample 6, Table 7)meta-nitroaniline EO (homopolymer of chromophore of this trifluoroethyl-invention methacrylate)

[0081] Table 10 presents electrooptic coefficient information for thethermoplastic polymer systems of the present invention. TABLE 10Electrooptic Coefficient Film Poling Poling Thickness TemperatureVoltage EO Coefficient System (um) ° C. (DC) (Pm/v) Disperse Red-1(conventional EO 1.8 95 120 2.6 chromophore) in polymethylmethacrylate(control) 3-nitroaniline (conventional EO 1.1 95 110 Could not bechromophore) in measured polymethylmethacrylate (control) (0.1<)4-fluoro-3-nitroaniline (EO 1.1 95 110 0.3 chromophore of thisinvention) in polymethylacrylate Sample 4 (Table 7) with Disperse 2.8 80150 1 Red-1 (conventional EO chromophore)

POLYMER EXAMPLE 4 Novel Thermosetting Polymers

[0082] A copolymer was prepared in a similar manner as described forPolymer Examples 2 and 3 but in this embodiment, part of themethylmethacrylate monomer (15%) was replaced with hydroxyethylacrylate. This copolymer contained approximately (all wt. %):

[0083] 60% trifluoroethylmethacrylate (monomer of low refractive indexn=1.361),

[0084] 15% methylmethacrylate (monomer of slightly higher refr. indexn=1.49),

[0085] 15% hydroxyethylmethacrylate (crosslinker),

[0086] 8% acrylonitrile (compatibility with chromophore),

[0087] 1% methacryloxypropyl-trimethoxy silane (adhesion promoter), and

[0088] 1% acrylic acid (adhesion promoter).

[0089] This polymer system was combined with a conventional EOchromophore (metanitroaniline) and a thermally activatedcondensation/transetherification crosslinking agent such ashexamethoxymelamine and dissolved in dioxane (1-5% solids). Thissolution was spun onto ITO coated quartz or glass slides and baked in anoven at 80° C. for 1 hr to effect the crosslinking reaction. This curedor crosslinked film had excellent solvent resistance while stillmaintaining a high degree of electrooptical activity. In contrast, allof the thermoplastic polymers of the prior art and this invention couldbe redissolved with solvent after applying to a substrate.

[0090] The system could also be combined with an EO chromophore of thisinvention with similar results.

POLYMER EXAMPLE 5 Direct Formation of Novel Thermosetting Polymers

[0091] In this example, a novel approach was used to create threepolymer systems that were highly suitable for fabrication of opticalswitch devices. In this examples, the following basic ingredients wereused:

[0092] trifluroethylmethacrylate (50%) (monomer for low refractiveindex),

[0093] ethyleneglycoldiacrylate (30%) (to cross-link and increaseT_(g)),

[0094] acrylonitrile (5%) (compatibility with chromophore), and

[0095] acrylic acid (1%) (adhesion promotion).

[0096] In a first and second reaction, the conventional EO chromophores(Disperse Red-1 or methacrylic acid ester of Disperse Red-1) were mixedwith and reacted with the basic ingredients. In a third reaction, afluorinated EO chromophore of this invention was combined to create a100% reactive liquid system. To this liquid reactive system was added afree radical initiator (benzoyl peroxide−2% by weight) and the catalyzedliquid system applied to a quartz waveguide, covered with a thin pieceof weighted Teflon film and heated in oven for 8 hours until fully curedinto a rigid solid highly crosslinked film having excellent adhesion tothe silica substrate. See Table 11 below. TABLE 11 Direct Formation ofNovel Thermosetting Polymers Sample Ingredients Free radical No. (wt %)EO chromophore initiator 1 trifluroethylmethacrylate Disperse Red-1benzoyl peroxide (50%) ethyleneglycoldiacrylate (30%) acrylonitrile (5%)acrylic acid (1%) 2 trifluroethylmethacrylate methacrylic acid benzoylperoxide (50%) ester of Disperse ethyleneglycoldiacrylate Red-1 (30%)acrylonitrile (5%) acrylic acid (1%) 3 trifluroethylmethacrylate4-fluoro-3- benzoyl peroxide (50%) nitroanaline ethyleneglycoldiacrylate(30%) acrylonitrile (5%) acrylic acid (1%)

POLYMER EXAMPLE 6 Other Fluorine Containing or Low Refractive IndexPolymer Systems

[0097] In alternative embodiments, the present invention is practicedusing different monomer building blocks (see Table 12 below) to createnew polymer systems other than those constructed using unsaturatedmonomer materials (Tables 2, 3, and 4). TABLE 12 Polyester, Polyamide,Polyurethane, Polyimide and Epoxy Monomers Monomers Refractive IndexAlkanediols and Fluorinated Alkanediols 1.43-1.46 Etherdiols andFluorinated polyetherdiols 1.44-1.46 Anhydrides 1.324-1.51  Dianhydrides— Diacids — Diamines 1.45 Epoxides 1.36-1.55 Diisocyanates 1.45-1.59Lactams and Lactones 1.41-1.48

POLYMER EXAMPLE 6A

[0098] In this example, a fluorine containing polyester resin wasprepared by combining one mole of tetrafluorosuccinic anhydride(n=1.320) and one mole of 2,2,3,3,4,4 hexafluoro 1,5-pentanediol or onemole of tetrafluorophthalic anhydride and ethylene glycol as shownbelow:

POLYMER EXAMPLE 6B

[0099] In this example, fluorine containing polyamides were produced byreacting one mole of a diamine (1,6 hexane diamine) with one mole of aperfluoropolyether diacid fluoride as shown below:

POLYMER EXAMPLE 6C

[0100] In this example, reactive epoxy resin systems were prepared byreacting equal parts of a fluorinated epoxy resin with a perfluorinateddianhydride as shown below:

POLYMER EXAMPLE 6D

[0101] For this example, fluorinated polyurethane polymers(thermoplastic or thermosetting) were produced in a similar manner asshown in the following reaction sequence.

POLYMER EXAMPLE 6E

[0102] In this example, fluorinated polyimides can be produced by thefollowing reaction sequence.

[0103] All of these previously described fluorine containing lowrefractive index polymer systems (polyesters, polyamides, polyimides,epoxy polymers, polyurethanes) can be further modified to containadhesion promotion functionality (—CN, —COOH, —Si(OMe)₃) and chemicallycombined EO chromophores.

POLYMER EXAMPLE 6F

[0104] This example illustrates modified polyesters of the presentinvention that can be prepared according to the following reactionsequence:

POLYMER EXAMPLE 6G Hybrid (Organic-inorganic) or Nanocomposite PolyesterPolymers

[0105] A hybrid polyester polymer was prepared according to theprocesses described by Rob Van Der Linde and Suzan Frings which waspresented at the 6^(th) Biennial North American Research Conference on“The Science and Technology of Organic Coatings” Nov. 5-8, 2000 at theWestin Resort Hotel, Hilton Head Island, S.C. (proceedings published bythe Institute of Materials Science—New Paltz—New York).

[0106] A hydroxy-terminated polyester was reacted with3-(triethoxysilyl) propyl isocyanate followed by further reaction withtetraethoxy silane and hexamethoxy melamine. The final result was ahighly transparent coating with good optical properties that can be usedin optical devices.

POLYMER EXAMPLE 6H Dendritic Polyester and Polyethers

[0107] Highly branched or dendritic polyesters can be made by thereaction of trimellitic anhydride with propylene oxide and the dendriticpolyethers can be prepared using benzyl halide derivatives or dihydroxybenzene (complete synthetic procedures and descriptions of functionaldendrimers, hyperbranched and star polymers can be found in Progress inPolymer Science, an International Review Journal May 2000, Vol 25, No.4, K. Inoue pages 453-571).

POLYMER EXAMPLE 6I Modified Polyurethane

[0108] Modified polyurethanes according to the invention can be preparedby the following reaction of low refractive index (preferablyn=1.43-1.46) fluorine containing diols, a polyisocyanate, an EOchromophore diol, and an adhesion promoter.

POLYMER EXAMPLE 6J Polyphosphazenes

[0109] According to the present invention, the preparation ofpolyphosphazenes systems is described in general terms as follows:

[0110] These polymers can be easily modified to be thermosetting,contain adhesive bonding capabilities as well as contain a covalentlybonded EO chromophore. The following structure represents the generalstructure of a preferred polymer according to the present invention:

[0111] wherein x₁=50-80%, x₂=10-15%, x₃=1-5%, x₄=5-20%

[0112] and wherein said percentages are by wt %. Further, any one ormore of the —F groups can be replaced by an —H group. Typically in apreferable embodiment of the invention, there is at least one —F atompresent. Preferably there are sufficient —F atoms present to obtain thedesired refractive index and compatibilization with EO chromophores.

POLYMER EXAMPLE 7 Polymer for Nonsilica Substrates Such as Glass andPlastics

[0113] The previously described polymer systems are designed to haverelatively low refractive index values but it is possible to designother polymer systems with higher refractive index values but with thesame critical requirements as described earlier. The desired profiles ofthese new polymers are shown in Table 13. TABLE 13 Comparison of thePrior Art High Refractive Index Polymers and the High Refractive IndexPolymers of this Invention Thermal Stability {cross- Water/ Ease EORefractive linking Moisture of Chromophore Index Tg capability}Sensitivity Poling Adhesion Compatibility Prior Art n > 1.5 100° C.>Variable Yes No Poor Highly {Variable} variable This n > 1.5 100° C.>Yes No Yes Excellent Excellent Example {Yes}

[0114] A copolymer for this invention was prepared by free radical(benzoyl peroxide or Azo-bisbutylnitrile) polymerization of (all wt. %):

[0115] 80% styrene monomer (base monomer),

[0116] 13% methylmethacrylate (base comonomer),

[0117] 5% acrylonitrile (EO compatibility), and

[0118] 2% methacryloxypropylsilane(trimethoxy) (adhesion promoter), intoluene solution (20% solids). The resultant polymer had a Tg of around100° C. and excellent adhesion to glass or polystyrene and polycarbonatesubstrates. A control polymer that only contained styrene andmethylmethacrylate did not have good adhesion to glass or plasticsubstrates. These particular polymers can be used with conventional EOchromophores, as well as the EO chromophores of this invention.

POLYMER EXAMPLE 8 Improved Flow

[0119] It has been discovered that small amounts of aromatic functionalgroups in or attached to the polymer backbone help in causing thepolymer in a solvent to wet and flow evenly to produce excellent thinfilm properties. For example, a 100% acrylic polymer(polymethylmethacrylate) dissolved in dioxane (20% solution) was spincoated onto glass slides and produced films that had a wide variety ofridges and structures. A copolymer of methylmethacrylate and 1% styrene(flow agent) resulted in a very thin film when spin cast out of dioxanebut these films had very little ridges or striations.

[0120] Similar results were observed for low refractive index polymersystems that contained small amounts of styrene or perfluorinatedstyrene monomers copolymerized with low refractive index acrylic monomermaterials. The addition of aromatics such as styrene or perfluorinatedstyrene (for the low refractive index system) provides the desiredimproved flow properties.

POLYMER EXAMPLE 9 Poling Efficiency

[0121] Polymers such as polymethylmethacrylate that contain EOchromophore (Disperse Red-1) generally require approximately 100 voltsper micron of film thickness to align or pole the EO chromophore. Otherfactors such as Tg, temperature and polymer molecular weight alsoinfluence the poling efficiency of a polymer and EO system.

[0122] It has been found that polymers containing —CF₃, —CN, and

[0123] functional groups in the range of 1 to 50% in or on theirbackbone structures can be used in lowering the poling voltage to below100 volts per micron film thickness.

[0124] Regarding thermoplastic and thermosetting polymers, the followingconclusions are apparent from the present invention:

[0125] (a) low refractive index fluoropolymers are not alone sufficientto create a durable host material for a guest or chemically bondedoptically active chromophore (prior art);

[0126] (b) combinations of fluorine containing monomers withnon-fluorine containing monomers allows one to maintain an acceptablerefractive index value and high Tg values for silica based opticalwaveguide systems (this invention);

[0127] (c) the use of optically active chromophore compatibilizationgroups (solubilization groups) provides materials with superiorproperties (1) for conventional chromophores, defined elsewhere herein,typical examples are nitrites (typical example, acrylonitrile), andesters, in some embodiments aromatics may be included; (2) forchromophores according to the present invention, defined elsewhereherein, typical examples include nitrites (typical example,acrylonitrile), fluorinated esters, and fluorinated aromatics;

[0128] (d) the use of adhesive promotion functional groups (typicalexamples include nitriles, silanes, fluorinated silanes, organic acids(e.g. carboxylic acids), fluorinated acids, alcohols, and fluorinatedalcohols, in some embodiments amides, amines, may be included) increasethe overall durability of the entire polymer system in a device (thisinvention);

[0129] (e) polymer electrical property control functional groups(typical examples are nitrites, aromatics) can be added to enhanceelectrical properties;

[0130] (f) water resistant functional groups (typical examples arestyrenes, cycloaliphatics) all increase the overall durability of theentire polymer system in a device (this invention); and

[0131] (g) the polymers (copolymers and blends of homopolymers withother homopolymers or copolymers) described in this invention can beused to create enhanced total systems (superior to the prior art) usingconventional high hydrocarbon content optically active chromophores.

[0132] Typically, and preferably the functional optical materialcontains between about 0.1 to about 20% of one or more compatibilizersas described above. Typically, the functional optical material containsbetween about 0.1 to about 10% of an adhesive promotion group, orcombination of adhesive promotion groups as described above.

[0133] When a particular compatibilizer can also perform some otherfunction (e.g. as an adhesion promoter) the best overall properties areobtained when a different material is added that performs the otherfunction, thus if a nitrile is used as a compatibilizer forchromophores, then another material such as a silane or fluorinatedsilane should be used for adhesion enhancement. While one alone wouldperform both functions, both materials together appear to performsynergistically to provide greatly enhanced performance over eitheralone.

[0134] The polymers of this invention are even more superior when thefluorinated optically active chromophores according to this inventionare used. In addition, the polymers of the present invention, asillustrated with the material from Sample 4 (Table 7) above, work withnonfluorinated materials as well.

[0135] II. Electrooptical Chromophores

[0136] The initial materials used in preparation of EO molecules of thisinvention were purchased from Aldrich Chemical Company P.O. Box 2060Milwaukee, Wis., 53201. For methods preferred in the preparation of theelectrooptical materials of this invention, see generally, Roy T. Holm,Journal of Paint Technology, Vol 39, No 509, June 1967 pages 385-388,and J. March, Advanced Organic Chemistry Reaction Mechanisms andStructures McGraw Hill Book Co. New York 1968.

[0137] The following reactions are representative of the generalchemistry of the preferred electrooptical materials of this invention.

Second Representative Reaction

R₁—NH₂→R₁N═N⁺X⁻+R₂→R₁—N═N—R₂

[0138] (aromatic) (aromatic)

R₁—F+Ph₃P═CH→R₁—CH═PPh₃

[0139] (aromatic)

R₁—CH═PPh₃+R₂CH→R₁CH═CHR₂

[0140] (aromatic)

Third Representative Reaction

R₁—F+CH₃NHC₂H₄OH→R₁NCH₃C₂H₄OH

[0141] (aromatic)

[0142] Typical electrooptic (EO) chromophores useful with the presentinvention are substituted anilines, substituted azobenzenes, substitutedstilbenes, or substituted imines as illustrated by the generalstructures shown below:

[0143] A. Substituted Anilines

[0144] Conventional Substituted Aniline EO Chromophores

[0145] Wherein D=donor=—NH₂, —N(CH₃)₂, —N(CH₂CH₃)₂, or —N(Y)₂ whereY=alkyl alcohols, alkyl (hydrocarbon fluorocarbon) esters, or alkylsilane derivatives;

A=acceptor=—NO₂, or —C(CN)C(CN)₂,

[0146] and

[0147] wherein X₁, X₂, X₃, X₄ are each —H.

[0148] Substituted Aniline EO Chromophores According to this Invention

[0149] Wherein D=donor=—NH₂, —N(CH₃)₂, —N(CH₂CH₃)₂, or —N(Y)₂ whereY=alkyl alcohols, alkyl (hydrocarbon fluorocarbon) esters, or alkylsilane derivatives;

[0150] A=acceptor=—NO₂, —C(CN)C(CN)₂, or —N═C(R1)(R2), wherein R₁=CF₃,C₂F₅, C_(n)F_(2n+1), R₂=H, CH₃, CF₃, C₂F₅

[0151] wherein when A==—NO₂, or —C(CN)C(CN)₂, then X₁, X₂, X₃, X₄ areeach independently selected from the group —F and —H, and at least one—F is selected, and when A=—N═C(R1)(R2), wherein R₁=CF₃, C₂F₅,C_(n)F_(2n+1), R₂=H, CH₃, CF₃, C₂F₅, then X₁, X₂, X₃, X₄ are eachindependently selected from the group —F and —H.

[0152] Additional Substituted Aniline EO Chromophores According to thisInvention

[0153] Wherein D=donor=—NH₂,—N(CH₃)₂,—N(CH₂CH₃)₂, or —N(Y)₂ whereY=alkyl alcohols, alkyl (hydrocarbon or fluorocarbon) esters, or alkylsilane derivatives;

[0154] primary acceptor=—NO₂, —C(CN)C(CN)₂, or —N═C(R1)(R2), whereR₁=CF₃, C₂F₅, C_(n)F_(2n+1), R₂=H, CH₃, CF₃, C₂F₅

[0155] secondary acceptor=—CN, or —CF₃

[0156] wherein if A₁ and A₂ are both primary acceptors selected from—NO₂, or —C(CN)C(CN)₂, then X₁, X₂, X₃ are each independently selectedfrom —F and —H, but at least one —F must be selected;

[0157] wherein if A₁ and A₂ are both secondary acceptors selected from—NO₂, or —C(CN)C(CN)₂, then X₁, X₂, X₃ are each independently selectedfrom —F and —H, but at least one —F must be selected;

[0158] wherein if A₁ and/or A₂ are selected from the primary acceptor—N═C(R1)(R2), where R₁=CF₃, C₂F₅, C_(n)F_(2n+1), R₂=H, CH₃, CF₃, C₂F₅,then X₁, X₂, X₃ are each independently selected from —F and —H; and

[0159] wherein if A₁ is selected from any primary acceptor, and A₂ isselected from any secondary acceptor, then X₁, X₂, X₃ are eachindependently selected from —F and —H.

[0160] B. Substituted Azobenzenes

[0161] Conventional Substituted Azobenzene EO Chromophores

[0162] Wherein D=donor=—NH₂,—N(CH₃)₂, —N(CH₂CH₃)₂, or —N(Y)₂ whereY=alkyl alcohols, alkyl (hydrocarbon fluorocarbon) esters, or alkylsilane derivatives;

[0163] A=acceptor=—NO₂, or —C(CN)C(CN)₂, and

[0164] wherein X₁, X₂, X₃, X₄ are each —H.

[0165] Substituted Azobenzene EO Chromophores According to thisInvention

[0166] Wherein D=donor=—NH₂, —N(CH₃)₂, —N(CH₂CH₃)₂, or —N(Y)₂ whereY=alkyl alcohols, alkyl (hydrocarbon fluorocarbon) esters, or alkylsilane derivatives;

[0167] A=acceptor=—NO₂, —C(CN)C(CN)₂, or —N═C(R1)(R2), wherein R₁=CF₃,C₂F₅, C_(n)F_(2n+1), R₂=H, CH₃, CF₃, C₂F₅

[0168] wherein when A==—NO₂, or —C(CN)C(CN)₂ , then X₁, X₂, X₃, X₄ areeach independently selected from the group —F and —H, and at least one—F is selected, and when A=—N═C(R1)(R2), wherein R₁=CF₃, C₂F₅,C_(n)F_(2n+1), R₂=H, CH₃, CF₃, C₂F₅, then X₁, X₂, X₃, X₄ are eachindependently selected from the group —F and —H.

[0169] Additional Substituted Azobenzene EO Chromophores According tothis Invention

[0170] Wherein D=donor=—NH₂, —N(CH₃)₂, —N(CH₂CH₃)₂, or —N(Y)₂ whereY=alkyl alcohols, alkyl (hydrocarbon or fluorocarbon) esters, or alkylsilane derivatives;

[0171] primary acceptor=—NO₂, —C(CN)C(CN)₂, or —N═C(R1)(R2), whereR₁=CF₃, C₂F₅, C_(n)F_(2n+1), R₂=H, CH₃, CF₃, C₂F₅

[0172] secondary acceptor=—CN, or —CF₃

[0173] wherein if A₁ and A₂ are both primary acceptors selected from—NO₂, or —C(CN)C(CN)₂, then X₁, X₂, X₃ are each independently selectedfrom —F and —H, but at least one —F must be selected;

[0174] wherein if A₁ and A₂ are both secondary acceptors selected from—NO₂, or —C(CN)C(CN)₂, then X₁, X₂, X₃ are each independently selectedfrom —F and —H, but at least one —F must be selected;

[0175] wherein if A₁ and/or A₂ are selected from the primary acceptor—N═C(R1)(R2), where R₁=CF₃, C₂F₅, C_(F) ₂n+₁, R₂=H, CH₃, CF₃, C₂F₅, thenX₁, X₂, X₃ are each independently selected from —F and —H; and

[0176] wherein if A₁ is selected from any primary acceptor, and A₂ isselected from any secondary acceptor, then X₁, X₂, X₃ are eachindependently selected from —F and —H.

[0177] C. Substituted Stilbenes

[0178] Conventional Substituted Stilbene EO Chromophores

[0179] Wherein D=donor=—NH₂, —N(CH₃)₂, —N(CH₂CH₃)₂, or —N(Y)₂ whereY=alkyl alcohols, alkyl (hydrocarbon fluorocarbon) esters, or alkylsilane derivatives;

[0180] A=acceptor=—NO₂, or —C(CN)C(CN)₂, and

[0181] wherein X₁, X₂, X₃, X₄ are each —H.

[0182] Substituted Stilbene EO Chromophores According to this Invention

[0183] Wherein D=donor=—NH₂, —N(CH₃)₂, —N(CH₂CH₃)₂, or —N(Y)₂ whereY=alkyl alcohols, alkyl (hydrocarbon fluorocarbon) esters, or alkylsilane derivatives;

[0184] A=acceptor=—NO₂, —C(CN)C(CN)₂, or —N═C(R1)(R2), wherein R₁=CF₃,C₂F₅, C_(n)F_(2n+1), R₂=H, CH₃, CF₃, C₂F₅

[0185] wherein when A==—NO₂, or —C(CN)C(CN)₂ , then X₁, X₂, X₃, X₄ areeach independently selected from the group —F and —H, and at least one—F is selected, and when A=—N═C(R1)(R2), wherein R₁=CF₃, C₂F₅,C_(n)F_(2n+1), R₂=H, CH₃, CF₃, C₂F₅, then X₁, X₂, X₃, X₄ are eachindependently selected from the group —F and —H.

[0186] Additional Substituted Stilbene EO Chromophores According to thisInvention

[0187] Wherein D=donor=—NH₂, —N(CH₃)₂, —N(CH₂CH₃)₂, or —N(Y)₂ whereY=alkyl alcohols, alkyl (hydrocarbon or fluorocarbon) esters, or alkylsilane derivatives;

[0188] primary acceptor=—NO₂, —C(CN)C(CN)₂, or —N═C (R1)(R2), whereR₁=CF₃, C₂F₅, C_(n)F_(2n+1), R₂=H, CH₃, CF₃, C₂F₅

[0189] secondary acceptor=—CN, or —CF₃

[0190] wherein if A₁ and A₂ are both primary acceptors selected from—NO₂, or —C(CN)C(CN)₂, then X₁, X₂, X₃ are each independently selectedfrom —F and —H, but at least one —F must be selected;

[0191] wherein if A₁ and A₂ are both secondary acceptors selected from—NO₂, or —C(CN)C(CN)₂, then X₁, X₂, X₃ are each independently selectedfrom —F and —H, but at least one —F must be selected;

[0192] wherein if A₁ and/or A₂ are selected from the primary acceptor—N═C(R1)(R2), where R₁=CF₃, C₂F₅, C_(n)F_(2n+1), R₂=H, CH₃, CF₃, C₂F₅,then X₁, X₂, X₃ are each independently selected from —F and —H; and

[0193] wherein if A₁ is selected from any primary acceptor, and A₂ isselected from any secondary acceptor, then X₁, X₂, X₃ are eachindependently selected from —F and —H.

[0194] D. Substituted Imines

[0195] Conventional Substituted Imine EO Chromophores

[0196] Wherein D=donor=—NH₂, —N(CH₃)₂, —N(CH₂CH₃)₂, or —N(Y)₂ whereY=alkyl alcohols, alkyl (hydrocarbon fluorocarbon) esters, or alkylsilane derivatives;

[0197] A=acceptor=—NO₂, or —C(CN)C(CN)₂, and

[0198] wherein X₁, X₂, X₃, X₄ are each —H.

[0199] Substituted Imine EO Chromophores According to this Invention

[0200] Wherein D=donor=—NH₂, —N(CH₃)₂, —N(CH₂CH₃)₂, or —N(Y)₂ whereY=alkyl alcohols, alkyl (hydrocarbon fluorocarbon) esters, or alkylsilane derivatives;

[0201] A=acceptor=—NO₂, —C(CN)C(CN)₂, or —N═C(R1)(R2), wherein R₁=CF₃,C₂F₅, C_(n)F_(2n+1), R₂=H, CH₃, CF₃, C₂F₅

[0202] wherein when A==—NO₂, or —C(CN)C(CN)₂, then X₁, X₂, X₃, X₄ areeach independently selected from the group —F and —H, and at least one—F is selected, and when A=—N═C(R1)(R2), wherein R₁=CF₃, C₂F₅,C_(n)F_(2n+1), R₂=H, CH₃, CF₃, C₂F₅, then X₁, X₂, X₃, X₄ are eachindependently selected from the group —F and —H.

[0203] Additional Substituted Imine EO Chromophores According to thisInvention

[0204] Wherein D=donor=—NH₂, —N(CH₃)₂, —N(CH₂CH₃)₂, or —N(Y)₂ whereY=alkyl alcohols, alkyl (hydrocarbon or fluorocarbon) esters, or alkylsilane derivatives;

[0205] primary acceptor=—NO₂, —C(CN)C(CN)₂, or —N═C(R1)(R2), whereR₁=CF₃, C₂F₅, C_(n)F_(2n+1), R₂=H, CH₃, CF₃, C₂F₅

[0206] secondary acceptor=—CN, or —CF₃

[0207] wherein if A₁ and A₂ are both primary acceptors selected from—NO₂, or —C(CN)C(CN)₂, then X₁, X₂, X₃ are each independently selectedfrom —F and —H, but at least one —F must be selected;

[0208] wherein if A₁ and A₂ are both secondary acceptors selected from—NO₂, or —C(CN)C(CN)₂, then X₁, X₂, X₃ are each independently selectedfrom —F and —H, but at least one —F must be selected;

[0209] wherein if A₁ and/or A₂ are selected from the primary acceptor—N═C(R1)(R2), where R₁=CF₃, C₂F₅, C_(n)F_(2n+1), R₂=H, CH₃, CF₃, C₂F₅,then X₁, X₂, X₃ are each independently selected from —F and —H; and

[0210] wherein if A₁ is selected from any primary acceptor, and A₂ isselected from any secondary acceptor, then X₁, X₂, X₃ are eachindependently selected from —F and —H.

EO Chromophore Example 1 Substituted Anilines

[0211] The following chemical structures in Table 14 are a comparison ofthe conventional to the electrooptical materials of the presentinvention and further aid in illustrating the invention. These EOmaterials are substituted anilines and are simplified versions of thegeneral formulas illustrated above. TABLE 14 Comparison of theConventional and the Present Invention Electrooptic Materials

Conventional

This invention

Conventional

This invention

This invention

[0212] Table 14 shows the presence and location of primary and secondaryelectron withdrawing groups as well as fluorine atoms for substitutedanilines. This embodiment of the invention has two typical types of EOchromophores as illustrated by the chemical structures. A first type ofEO chromophore of the invention includes a substituted aniline having atleast one primary or at least one secondary electron withdrawing group,and at least one fluorine group on the aromatic ring. A second type ofEO chromophore of the invention includes a substituted aniline having atleast one primary and at least one secondary electron withdrawing groupon the aromatic ring. A third type of EO chromophore of the inventionincludes a substituted aniline having at least one primary and at leastone secondary electron withdrawing group on the aromatic ring, and atleast one fluorine atom on the on the aromatic ring. The primaryelectron withdrawing groups are typically selected from the groupconsisting of —NO₂ and —C(CN)C(CN)₂. The secondary electron withdrawinggroups are typically selected from the group consisting of —CN, and—CF₃. These and other groups are illustrated in more detail elsewhereherein. The location of the electron withdrawing groups and the fluorineatoms may be in any position of the aromatic ring; however, sites forobtaining or maintaining selected properties are determined byprocedures described in more detail below.

EO Chromophore Example 2 Substituted Stilbenes, Imines, and Azobenzenes

[0213] The following chemical structures in Table 15 are a comparison ofthe conventional to the electrooptical materials of the presentinvention. These EO materials are substituted stilbenes, substitutedimines, and substituted azobenzenes. TABLE 15 Comparison of theConventional and the Present Invention Electrooptic Materials

Conventional

Conventional

This invention

This invention

Conventional

Conventional

This invention

This invention

This invention

This invention Note:

Primary = —NO₂, —C(CN)C(CN)₂, —N═C(R1)(R2), where R₁ = CF₃, C₂F₅,C_(n)F_(2n+1), R₂ = H, CH₃, CF₃, C₂F₅ Secondary = —CN, —CF₃

EO Chromophore Example 3 Substituted Anilines, Stilbenes, Imines, andAzobenzenes

[0214] The fundamental structures for conventional optically activechromophores and optically active chromophores of the present inventionhave been given in detail herein. In EO chromophores of the presentinvention, fluorine atoms are typically strategically placed on thearomatic ring so that the EO coefficient, which is directly related toμβ (vector product of the dipole moment times the firsthyperpolarizability of the molecule), is increased or is notsubstantially reduced. The dipole moments and firsthyperpolarizabilities were calculated using ab initio electronicstructure methods as implemented in JAGUAR™ (Jaguar 4.0, SchrodingerInc., Portland, Oreg., 1991-2000). Ab initio methods have been shown toprovide accurate descriptions of the hyperpolarizabilities in aromaticmolecules. Direct comparison of experimental and calculated μβ valuesfor a trial set of 54 organic molecules has shown this method toaccurately determine the μβ product for organic molecules of the generaltype considered in this invention. The tensor components of the firsthyperpolarizability were determined by the coupled-perturbedHartree-Fock method implemented in JAGUAR™. Only the vector product ofthe hyperpolarizability with the intrinsic dipole (μβ) is reported andnoted in the tables, as this is the quantity of direct relevance to theEO coefficient of a chromophore. A description of how this criticalplacement of fluorine atoms influences the μβ ∞ EO coefficient is shownin Table 16. All the reported μβ values are in units of 10⁻⁴⁸ esu. Therelative rankings for these EO materials are calculated as follows:

Relative Ranking (R)=μβ(all —H or —F substituted EO molecule)/μβ(all —HEO molecule)

[0215] Thus for paranitroaniline (Table 16)$R = {\frac{54.7}{54.7} = 1.00}$

[0216] For 2,6-difluoro-4-nitroaniline $R = {\frac{45.9}{54.7} = 0.84}$

[0217] In some cases a fluorine-substituted EO molecule may have a lowerμβ coefficient than the all hydrogen EO chromophore. The all hydrogen EOchromophore, however, increases the overall total refractive index ofthe system (which is undesirable when low refractive indexes arerequired) as well as introduces a higher level of optical loss (C—Hbonds, N—H bonds, O—H bonds) to the total systems than its fluorinatedcounterpart. Thus, in selecting which EO chromophore structure to useone can trade-off the EO coefficient property of a molecule with itsability to enhance the total properties of the entire system.

[0218] Analysis of Fluorine Atom Substitution Effects on StructuresShown in Table 16 for Selected Properties

[0219] Para (4)—Nitroaniline

[0220] Two fluorine atoms on the 3,5 positions (46.0) are slightlybetter than on the 2,6 positions (45.9). Four fluorine atoms on the2,3,5,6 position are less desirable (45.6) than other combinations.

[0221] Meta (3)—Nitroaniline

[0222] One fluorine atom on the 6 position (18.7) is better than onefluorine atom on the 2 position (9.84).

[0223] Four fluorine atoms on the 2, 4, 5, 6 positions are lessdesirable (15.9) than substitution at the 6 position.

4-(4-nitrophenylazo)phenylamine

[0224]

[0225] One fluorine atom on the 2 position of the 4-nitrophenylazo groupis less desirable (242.1) than a fluorine atom on the 3 position (458.1)of the 4-nitrophenylazo group.

[0226] Four fluorine atoms on the 2,3,5,6 position of the4-nitrophenylazo group is better (350.6) than four fluorine atoms onboth the 4-nitrophenylazo group and the phenylamine group (a total of 8fluorine atoms resulting in a value of 216.0).

4—Nitrophenyl, 4-aminophenyl stilbene

[0227]

[0228] One fluorine atom on the 2 position of the 4-nitrophenyl group isless desirable (325.6) than one fluorine atom on the 3 position of the4-nitrophenyl group (355.0).

[0229] Four fluorine atoms on the 2,3,5,6 position of the 4-nitrophenylgroup is more desirable (520.8) than four fluorine atoms both on the4-nitrophenly group and the phenylamine group (a total of 8 fluorineatoms resulting in a value of 209.1).

[0230] Similar results were observed for stilbene having the followingstructure.

TABLE 16 EO Molecules Relative Structure μβ Ranking Comments

54.7 1.00 Conventional

46.0 0.84 This invention

45.9 0.84 This invention

45.6 0.83 This invention

14.3 1.00 Conventional

18.7 1.31 This invention

9.84 0.69 This invention

15.9 1.11 This invention

287.2 1.00 Conventional

242.1 0.84 This invention

458.1 1.60 This invention

350.6 1.22 This invention

216.9 0.76 This invention

381.1 1.00 Conventional

325.6 0.85 This invention

355.0 0.93 This invention

520.8 1.37 This invention

209.1 0.55 This invention

737.9 1.00 Conventional

666.0 0.90 This invention

830.0 1.12 This invention

640.1 0.87 This invention

356.5 0.48 This invention

[0231] Similar μβ and rankings can be generated for the following EOmolecules.

[0232] Where X₁ and X₂ can be independently selected to be an H or Fatom.

[0233] Critical Parameters for EO Chromophores with Low IndexApplications

[0234] The critical parameters for an EO molecule are its overallrefractive index, number of C—H bonds (optical loss), EO coefficient andspatial or geometric placement of donor/acceptor and other functionalgroups in its molecular structure. In the present invention, it isdemonstrated herein that the EO chromophore for the polymers used insilica optical applications have to be selected to be “compatible” withthe low refractive index polymers, contribute to the reduction of thetotal refractive index of the total system and still maintain a high EOcoefficient. Typically, EO chromophores have at least one —F group at anappropriate site or a fluorine containing electron acceptor. Thus,overall EO design is a function of {polymer compatibility; low overallcontribution to the total refractive index of the system, high EOefficiency}.

EO Chromophore Example 4 Perfluorinated Alkyl-Imines

[0235] A further embodiment of this invention is also based on thefollowing novel structures:

[0236] where

[0237] R₁=—CF₃, —C₂F₅, —C_(n)F_(2n+1)

[0238] R₂=—H, —CH₃,—CF₃, —C₂F₅

[0239] S=—N═N—, —CH═N—, —N═CH—, —CH═CH—.

[0240] One mole of methylheptafluoropropyl ketone or one mole ofperfluoro-2-heptanone

[0241] was mixed with excess (1.5 moles) of paraphenylenediamine

[0242] in toluene and reacted (thermal stripping of water) to producethe following new classes of EO materials.

[0243] The predicted EO efficiencies (μβ) for these two compounds are18.5 and 60.3. For further details as to production of these compounds,see the J. March reference noted earlier.

EO Chromophore Example 5 Primary and Secondary Electron WithdrawingGroups on EO Chromophores

[0244] The present invention is also based on the concept of combining aprimary electron withdrawing group (acceptor) with what is defined as asecondary electron withdrawing molecule. The primary electronwithdrawing groups (acceptors) are as follows: —NO₂

[0245] And the secondary electron withdrawing groups are as follows:

[0246] —CN—CF₃

[0247] This embodiment of the invention illustrates the importance ofselecting an EO chromophore with the primary and secondary electronwithdrawing group in the correct positions in order to maximize the EOeffect (μβ). The conventional appears to deal with one primary, onesecondary, two primary, or two secondary electron withdrawing groups,but not a combination of at least one primary and at least one secondaryelectron withdrawing groups. Table 17 illustrates the effect of multiplesubstitutions of primary and secondary electron withdrawing groups onspecific sites of an aniline molecule. This embodiment is alsoillustrated in Tables 14 and 15 for substituted anilines, substitutedstilbenes, substituted imines, and substituted azobenzenes. TABLE 17 EOMolecules of this Invention Relative Structure μβ Ranking Comments

54.7 1.00 Conventional

27.3 0.50 Conventional

57.7 1.05 This invention

30.6 0.56 This invention

10.3 0.19 Conventional

51.9 0.95 This invention

38.0 0.69 This invention

29.0 0.53 Conventional

37.4 0.68 Conventional

37.2 0.68 This invention

45.5 0.83 This invention

31.8 0.58 This invention

17.8 0.33 This invention

System Example 1

[0248] In a less complex embodiment, the optically active chromophoresare physically blended with the polymer, preferably in solvents, spinapplied into thin dry films onto appropriate substrates, followed by theapplication of electrodes, and then poling the films at highertemperatures followed by cooling to produce the final product. In a morecomplex embodiment, the optically active chromophore has a functionalgroup on the molecule that can be copolymerized into the polymer networkin order to create a more durable and stable system.

[0249] For example, for crosslinking, the optically active chromophoreshould contain the functional groups represented in the chemicalstructure below: (For further details, for modification of opticallyactive (EO) chromophores to contain reactive functional groups, see theJ. March reference noted earlier.):

[0250] —CH═CH₂

[0251] —OH

[0252] —COOH

[0253] Examples of preferred polymer/electrooptical chromophore systemsare represented by the following chemical structures. The structure onthe left represents the blending of a polymer with an optically activechromophore, while the structure on the right represents thecopolymerization of a polymer with an optically active chromophore.

[0254] (See Polymer Example 5, Sample 2 of this invention).

System Example 2 Relationship Between Adhesion, Optically ActiveChromophore Compatibility and Optical Loss Quality

[0255] The use of adhesion promotion agents (silanes, acids, hydroxylsand other carbon-hydrogen bond materials) does increase the overalldurability of the polymer/substrate system. The problem, however, isthat using these types of traditional adhesion promotion agents also candecrease the optical quality of the total system and decrease thestability or effectiveness of the optically active chromophore.

[0256] The present invention provides a unique combination of a nitrilegroup (CN) in combination with silane or fluorosilane coupling agentswhich not only reduces the amount of silane needed for adhesion butimproves the optical quality and EO efficiency of the total system.Table 18 illustrates this effect. TABLE 18 Adhesion Promotion SystemResults No Silane added to the polymer No adhesion, good opticalbackbone for adhesion quality poor EO compatibility Silane added to thepolymer backbone Good adhesion, poor optical for adhesion. quality, poorEO compatibility. Fluorosilane added to the polymer Good adhesion, goodoptical backbone for adhesion. quality, poor EO compatibility. Nitrileadded to the polymer backbone. Small amount of adhesion good opticalquality, good EO compatibility. Combination of silanes or fluorosilanesExcellent adhesion, excellent added to the polymer backbone alongoptical quality and EO with the nitrile group. compatibility.

System Example 3 Thermooptic Switch

[0257] This example illustrates that the functional optical materials ofthe present invention are useful in thermooptic switches. Referring tothe Drawing, a typical plastic optical fiber having a polymethacrylatecore 101 and a fluoropolymer cladding 102 was treated withtetrahydrofuran solvent to partially remove the cladding 102 at segment103 and expose the core 101. The plastic optical fiber was ordered fromEdmund Scientific, Industrial Optics Division, USA, Stock No. D2531™,and had a core diameter of 240 microns, while the total fiber diameterwas 250 microns. The core 101 consisted of polymethyl-methacrylate(refractive index of 1.492) and the cladding 102 consisted of afluorinated polymer (refractive index of 1.402). The core 101 of thefiber at segment 103 was then overcoated with a functional opticalmaterial 105 made from polymers and optically active chromophores ofthis invention to form a modified fiber 100. The polymers and opticallyactive chromophores were those illustrated in Polymer Example 2. Boththe conventional EO chromophore (metanitroaniline or Disperse Red-1) andthe EO chromophores of this invention were used in these tests.

[0258] Referring again to the Drawing, the modified fiber 100 was placedin a test apparatus 150, in order to measure the thermoopticalproperties of the functional optical material 105 of this invention.Test apparatus 150 consisted of a heating block 152 that held themodified fiber 100. The heating block was made up of an electricalheating coil (not shown) and connected to a source of electrical power154. A thermocouple 160 was mounted to the functional optical material105 to allow temperature measurements. The thermocouple 160 wasconnected to a display unit 162 for amplification of the signal anddisplay. A light source 170 was used to send a light 172 into one end ofthe modified fiber 100 and a light detector detected light 176 that hadpassed through the modified fiber 100.

[0259] The core 101 consisting of polymethylmethacrylate had arefractive index of about 1.49. The functional optical material 105 wasadjusted to have a refractive index of about 1.49 to about 1.5 at roomtemperature. Upon heating the modified fiber 100 the overall refractiveindex of the modified fiber 100 decreased.

[0260] At room temperature there was only a small amount of light beingtransmitted through core 101 of modified fiber 100. When the segment 103containing functional optical material 105 was heated, the refractiveindex was lowered and more light was transmitted through the modifiedfiber 100. Cooling the modified fiber 100 back to room temperatureresulted in a higher refractive index segment and thus less light wasguided in the core resulting in a lower intensity output. Thus, thethermooptic light intensity modulation was reversible.

[0261] An electrooptic switch or modulator could be made using the samematerials with slightly different ratios of compounds and with theapplication of electrodes. Electrooptic switches and modulators are wellknown in the art so that once knowing the teachings of the presentinvention the fabrication of an electrooptic switch or electroopticmodulator with the herein disclosed materials will be within the skillof the person of ordinary skill in the art. Typical applications inwhich the functional optical materials of the invention may be used aredisclosed in: U.S. Pat. No. 5,857,039 to Bosc; U.S. Pat. No. 5,659,010to Sotoyama et al.; U.S. Pat. No. 5,818,983 to Yoshimura et al.; U.S.Pat. No. 3,589,794 to Marcatili; and Dielectric Rectangular Waveguideand Directional Coupler for Integrated Optics, E. A. J. Marcatili, BellSyst. Tech. 3. vol. 48, pp.2071-2102, September 1969.

[0262] While the forms of the invention herein disclosed constitutepresently preferred embodiments, many others are possible. It is notintended herein to mention all of the possible equivalent forms orramifications of the invention. It is to be understood that the termsused herein are merely descriptive, rather than limiting, and thatvarious changes may be made without departing from the spirit of thescope of the invention.

We claim:
 1. A functional optical material for use in an optical system,comprising: (a) a polymer selected from the group comprising, (1) athermoplastic polymer; (2) a thermosetting polymer; and (3) acombination of thermoplastic and thermosetting polymers; wherein saidthermoplastic and/or thermosetting polymers contain carbon-hydrogenand/or carbon-fluoride functionality; and (b) one or more opticallyactive chromophores blended and/or copolymerized with said polymer; (c)a compatibilizer copolymerized with said polymer of step (a), having oneor more pendant groups selected from the group consisting of nitriles,esters, aromatics; fluorinated esters, and fluorinated aromatics; and(d) an adhesion promoter copolymerized with said polymer of step (a),having one or more pendant groups selected from the group consisting ofnitrites, silanes, fluorinated silanes, organic acids; fluorinatedorganic acids, alcohols, fluorinated alcohols, amides, and amines; andwherein when a compatibilizer with one particular pendant group isselected, an adhesion promoter with a different pendant group isselected.
 2. The functional optical material according to claim 1,wherein said thermoplastic and/or thermosetting polymer is selected fromthe group consisting of acrylics/methacrylics; copolymers of acrylicacid esters, methacrylic acid esters, and other single unsaturatedmonomers; polyesters; polyurethanes; polyimides; polyamides;polyphosphazenes; epoxy resin; and hybrid (organic-inorganic) ornanocomposite polyester polymers.
 3. The functional optical materialaccording to claim 1, wherein said thermoplastic polymer is selectedfrom the group consisting of acrylics/methacrylics (copolymers of estersof acrylic and methacrylic acid where the alcohol portion of the estercan be based on hydrocarbon, or partially or fully fluorinated alkylchains); polyesters (where the diacid or diol can containcarbon-hydrogen aliphatic, aromatic or carbon-fluorine functionality);polyurethanes (where the diisocyanate can be aliphatic or aromatic andthe diol can contain carbon-hydrogen or carbon-fluorine functionality);polyimides where the acid, amine, or diamine can be partially or fullyfluorinated; polyamides (where the diacid or diamine can containcarbon-hydrogen aliphatic, aromatic or carbon-fluorine functionality);polyphosphazenes (where the polyphosphazene backbone structure cancontain fluorinated aromatic or aliphatic functional groups, as well as,carbon-hydrogen functionality); epoxy resin (where the epoxy resin cancontain carbon-hydrogen or carbon-fluorine functionalityO which canfurther be reacted with diacids or anhydrides (that also containcarbon-hydrogen or carbon-fluorine functionality); and hybrid(organic-inorganic) or nanocomposite polyester polymers (where thepolyester component consists of aliphatic, aromatic carbon hydrogen orcarbon-fluorine functionality and the inorganic components are based onsilane or organometallic materials such as titanates, zirconates andother multivalent metal organics).
 4. The functional optical materialaccording to claim 1, wherein functional optical material has a glasstransition temperature above 100° C.
 5. The functional optical materialaccording to claim 1, wherein said functional optical material has arefractive index value of less than about 1.5.
 6. The functional opticalmaterial according to claim 1, wherein said functional optical materialhas a refractive index value of greater than or equal to about 1.5. 7.The functional optical material according to claim 1, wherein saidfunctional optical material has between 0.1 and 10% of a promoter havingan adhesive promotion group, or combination of adhesive promotiongroups.
 8. The functional optical material according to claim 1, whereinsaid compatibilizer has nitrile, ester, fluorinated ester, andfluorinated aromatic groups.
 9. The functional optical materialaccording to claim 1, wherein said adhesion promoter has nitrile,silane, fluorinated silane, organic acid; fluorinated organic acid,alcohol, and fluorinated alcohol groups.
 10. The functional opticalmaterial according to claim 1, wherein monomers are included thatprovide water resistance by having styrene and/or cycloaliphatic groups.11. The functional optical material according to claim 1, wherein saidsaid functional optical material has between 0.1 and 20% of one or morecompatibilizers for said one or more chromophores.
 12. The functionaloptical material according to claim 1, wherein there is less than 5 wt.% of hydrogen in the monomer repeat unit and other units of thefunctional optical material).
 13. The functional optical materialaccording to claim 1, wherein said functional optical material has lessthan 2% water absorption according to a 24 hour water immersion test.14. The functional optical material according to claim 1, wherein saidfunctional optical material requires less than 100 volts per micron offilm thickness to pole said functional optical material.
 15. Thefunctional material according to claim 1, wherein a compatibilizer isselected having a nitrile group, and an adhesion promoter is selectedhaving a silane group.
 16. The functional optical material according toclaim 1, wherein said one or more optically active chromophores is (are)selected from the group consisting of a substituted aniline, substitutedazobenzene, substituted stilbene, or substituted imine.
 17. Thefunctional optical material according to claim 16, wherein said one ormore optically active chromophores are selected from substitutedanilines comprising: first substituted anilines,

 Wherein D=donor=—NH₂, —N(CH₃)₂, —N(CH₂CH₃)₂, or —N(Y)₂ where Y=alkylalcohols, alkyl (hydrocarbon fluorocarbon) esters, or alkyl silanederivatives; A=acceptor=—NO₂, —C(CN)C(CN)₂, or —N═C(R1)(R2), whereinR₁=CF₃, C₂F₅, C_(n)F_(2n+1), R₂=H, CH₃, CF₃, C₂F₅ wherein when A==—NO₂,or —C(CN)C(CN)₂, then X₁, X₂, X₃, X₄ are each independently selectedfrom the group —F and —H, and at least one —F is selected, and whenA=—N═C(R1)(R2), wherein R₁=CF₃, C₂F₅, C_(n)F_(2n+1), R₂=H, CH₃, CF₃,C₂F₅, then X₁, X₂, X₃, X₄ are each independently selected from the group—F and —H; or second substituted anilines,

 Wherein D=donor=—NH₂, —N(CH₃)₂, —N(CH₂CH₃)₂, or —N(Y)₂ where Y=alkylalcohols, alkyl (hydrocarbon or fluorocarbon) esters, or alkyl silanederivatives; A₁=primary acceptor=—NO₂, —C(CN)C(CN)₂, or —N═C (R1)(R2),where R₁=CF₃, C₂F₅, C_(n)F_(2n+1), R₂=H, CH₃, CF₃, C₂F₅ A₂=secondaryacceptor=—CN, or —CF₃ wherein X₁, X₂, X₃ are each independently selectedfrom the group —F and —H; and wherein A₁ can be the same as A₂, whereintwo identical or different acceptors may be selected from group A1 ortwo identical or different acceptors may be selected from group A₂, sothat when acceptors are selected from —NO₂, —C(CN)C(CN)₂, —CN, or —CF₃,then X₁, X₂, X₃ are each independently selected from the group —F and—H, and at least one —F is selected; and if at least one acceptor isselected as —N═C (R1)(R2), where R₁=CF₃, C₂F₅, C_(n)F_(2n+1), R₂=H, CH₃,CF₃, C₂F₅, then X₁, X₂, X₃ are each independently selected from thegroup —F and —H.
 18. The functional optical material according to claim16, wherein said one or more optically active chromophores is (are)selected from substituted azobenzenes comprising: first substitutedazobenzenes,

 Wherein D=donor=—NH₂, —N(CH₃)₂, —N(CH₂CH₃)₂, or —N(Y)₂ where Y=alkylalcohols, alkyl (hydrocarbon fluorocarbon) esters, or alkyl silanederivatives; A=acceptor=—NO₂, —C(CN)C(CN)₂, or —N═C(R1)(R2), whereinR₁=CF₃, C₂F₅, C_(n)F_(2n+1), R₂=H, CH₃, CF₃, C₂F₅ wherein when A==—NO₂,or —C(CN)C(CN)₂, then X₁, X₂, X₃, X₄ are each independently selectedfrom the group —F and —H, and at least one —F is selected, and whenA=—N═C(R1)(R2), wherein R₁=CF₃, C₂F₅, C_(n)F_(2n+1), R₂=H, CH₃, CF₃,C₂F₅, then X₁, X₂, X₃, X₄ are each independently selected from the group—F and —H; or second substituted azobenzenes,

 Wherein D=donor=—NH₂, —N(CH₃)₂, —N(CH₂CH₃)₂, or —N(Y)₂ where Y=alkylalcohols, alkyl (hydrocarbon or fluorocarbon) esters, or alkyl silanederivatives; primary acceptor=—NO₂, —C(CN)C(CN)₂, or —N═C (R1)(R2),where R₁=CF₃, C₂F₅, C_(n)F_(2n+1), R₂=H, CH₃, CF₃, C₂F₅ secondaryacceptor=—CN, or —CF₃ wherein if A₁ and A₂ are both primary acceptorsselected from —NO₂, or —C(CN)C(CN)₂, then X₁, X₂, X₃ are eachindependently selected from —F and —H, but at least one —F must beselected; wherein if A₁ and A₂ are both secondary acceptors selectedfrom —NO₂, or —C(CN)C(CN)₂, then X₁, X₂, X₃ are each independentlyselected from —F and —H, but at least one —F must be selected; whereinif A₁ and/or A₂ are selected from the primary acceptor —N═C (R1)(R2),where R₁=CF₃, C₂F₅, C_(n)F_(2n+1), R₂=H, CH₃, CF₃, C₂F₅, then X₁, X₂, X₃are each independently selected from —F and —H; and wherein if A₁ isselected from any primary acceptor, and A₂ is selected from anysecondary acceptor, then X₁, X₂, X₃ are each independently selected from—F and —H.
 19. The functional optical material according to claim 16,wherein said one or more optically active chromophores is (are) selectedfrom substituted stilbenes comprising: first substituted stilbenes,

 Wherein D=donor=—NH₂, —N(CH₃)₂, —N(CH₂CH₃)₂, or —N(Y)₂ where Y=alkylalcohols, alkyl (hydrocarbon fluorocarbon) esters, or alkyl silanederivatives; A=acceptor=—NO₂, —C(CN)C(CN)₂, or —N═C(R1)(R2), whereinR₁=CF₃, C₂F₅, C_(n)F_(2n+1), R₂=H, CH₃, CF₃, C₂F₅ wherein when A==—NO₂,or —C(CN)C(CN)₂, then X₁, X₂, X₃, X₄ are each independently selectedfrom the group —F and —H, and at least one —F is selected, and whenA=—N═C(R1)(R2), wherein R₁=CF₃, C₂F₅, C_(n)F_(2n+1), R₂=H, CH₃, CF₃,C₂F₅, then X₁, X₂, X₃, X₄ are each independently selected from the group—F and —H; or second substituted stilbenes,

 Wherein D=donor=—NH₂, —N(CH₃)₂, —N(CH₂CH₃)₂, or —N(Y)₂ where Y=alkylalcohols, alkyl (hydrocarbon or fluorocarbon) esters, or alkyl silanederivatives; primary acceptor=—NO₂, —C(CN)C(CN)₂, or —N═C (R1)(R2),where R₁=CF₃, C₂F₅, C_(n)F_(2n+1), R₂=H, CH₃, CF₃, C₂F₅ secondaryacceptor=—CN, or —CF₃ wherein if A₁ and A₂ are both primary acceptorsselected from —NO₂, or —C(CN)C(CN)₂, then X₁, X₂, X₃ are eachindependently selected from —F and —H, but at least one —F must beselected; wherein if A₁ and A₂ are both secondary acceptors selectedfrom —NO₂, or —C(CN)C(CN)₂, then X₁, X₂, X₃ are each independentlyselected from —F and —H, but at least one —F must be selected; whereinif A₁ and/or A₂ are selected from the primary acceptor —N═C (R1)(R2),where R₁=CF₃, C₂F₅, C_(n)F_(2n+1), R₂=H, CH₃, CF₃, C₂F₅, then X₁, X₂, X₃are each independently selected from —F and —H; and wherein if A₁ isselected from any primary acceptor, and A₂ is selected from anysecondary acceptor, then X₁, X₂, X₃ are each independently selected from—F and —H.
 20. The functional optical material according to claim 16,wherein said one or more optically active chromophores is (are) selectedfrom substituted imines comprising: first substituted imines,

 Wherein D=donor=—NH₂, —N(CH₃)₂, —N(CH₂CH₃)₂, or —N(Y)₂ where Y=alkylalcohols, alkyl (hydrocarbon fluorocarbon) esters, or alkyl silanederivatives; A=acceptor=—NO₂, —C(CN)C(CN)₂, or —N═C(R1)(R2), whereinR₁=CF₃, C₂F₅, C_(n)F_(2n+1), R₂=H, CH₃, CF₃, C₂F₅ wherein when A==—NO₂,or —C(CN)C(CN)₂, then X₁, X₂, X₃, X₄ are each independently selectedfrom the group —F and —H, and at least one —F is selected, and whenA=—N═C(R1)(R2), wherein R₁=CF₃, C₂F₅, C_(n)F_(2n+1), R₂=H, CH₃, CF₃,C₂F₅, then X₁, X₂, X₃, X₄ are each independently selected from the group—F and —H; or second substituted imines,

 Wherein D=donor=—NH₂, —N(CH₃)₂, —N(CH₂CH₃)₂, or —N(Y)₂ where Y=alkylalcohols, alkyl (hydrocarbon or fluorocarbon) esters, or alkyl silanederivatives; primary acceptor=—NO₂, —C(CN)C(CN)₂, or —N═C (R1)(R2),where R₁=CF₃, C₂F₅, C_(n)F_(2n+1), R₂=H, CH₃, CF₃, C₂F₅ secondaryacceptor=—CN, or —CF₃ wherein if A₁ and A₂ are both primary acceptorsselected from —NO₂, or —C(CN)C(CN)₂, then X₁, X₂, X₃ are eachindependently selected from —F and —H, but at least one —F must beselected; wherein if A₁ and A₂ are both secondary acceptors selectedfrom —NO₂, or —C(CN)C(CN)₂, then X₁, X₂, X₃ are each independentlyselected from —F and —H, but at least one —F must be selected; whereinif A₁ and/or A₂ are selected from the primary acceptor —N═C (R1)(R2),where R₁=CF₃, C₂F₅, C_(n)F_(2n+1), R₂=H, CH₃, CF₃, C₂F₅, then X₁, X₂, X₃are each independently selected from —F and —H; and wherein if A₁ isselected from any primary acceptor, and A₂ is selected from anysecondary acceptor, then X₁, X₂, X₃ are each independently selected from—F and —H.
 21. The functional optical material according to claim 16,wherein one of said optically active chromophores comprises:


22. The functional optical material according to claim 16, wherein oneof said optically active chromophores comprises:


23. The functional optical material according to claim 16, wherein saidcompatibilizer has a nitrile group, and said one or more opticallyactive chromophores are selected from conventional substituted anilinescomprising:

Wherein D=donor=—NH₂, —N(CH₃)₂, —N(CH₂CH₃)₂, or —N(Y)₂ where Y=alkylalcohols, alkyl (hydrocarbon fluorocarbon) esters, or alkyl silanederivatives; A=acceptor=—NO₂, or —C(CN)C(CN)₂, and wherein X₁, X₂, X₃,X₄ are each —H.
 24. The functional optical material according to claim16, wherein said one or more optically active chromophores is (are)selected from conventional substituted azobenzenes comprising:

Wherein D=donor=—NH₂, —N(CH₃)₂, —N(CH₂CH₃)₂, or —N(Y)₂ where Y=alkylalcohols, alkyl (hydrocarbon fluorocarbon) esters, or alkyl silanederivatives; A=acceptor=—NO₂, or —C(CN)C(CN)₂, and wherein X₁, X₂, X₃,X₄ are each —H.
 25. The functional optical material according to claim16, wherein said one or more optically active chromophores is (are)selected from conventional substituted stilbenes comprising:

Wherein D=donor=—NH₂, —N(CH₃)₂, —N(CH₂CH₃)₂, or —N(Y)₂ where Y=alkylalcohols, alkyl (hydrocarbon fluorocarbon) esters, or alkyl silanederivatives; A=acceptor=—NO₂, or —C(CN)C(CN)₂, and wherein X₁, X₂, X₃,X₄ are each —H.
 26. The functional optical material according to claim16, wherein said one or more optically active chromophores is (are)selected from conventional substituted imines comprising:

Wherein D=donor=—NH₂, —N(CH₃)₂, —N(CH₂CH₃)₂, or —N(Y)₂ where Y=alkylalcohols, alkyl (hydrocarbon fluorocarbon) esters, or alkyl silanederivatives; A=acceptor=—NO₂, or —C(CN)C(CN)₂, and wherein X₁, X₂, X₃,X₄ are each —H.
 27. A functional optical material for use in an opticalsystem, comprising: (a) a polymer selected from the group comprising,(1) a thermoplastic polymer; (2) a thermosetting polymer; and (3) acombination of thermoplastic and thermosetting polymers; wherein saidthermoplastic and/or thermosetting polymers contain carbon-hydrogenand/or carbon-fluoride functionality; and (b) one or more opticallyactive chromophores blended and/or copolymerized with said polymer,wherein said chromophore comprises: first substituted anilines

 Wherein D=donor=—NH₂, —N(CH₃)₂, —N(CH₂CH₃)₂, or —N(Y)₂ where Y=alkylalcohols, alkyl (hydrocarbon fluorocarbon) esters, or alkyl silanederivatives; A=acceptor=—NO₂, —C(CN)C(CN)₂, or —N═C(R1)(R2), whereinR₁=CF₃, C₂F₅, C_(n)F_(2n+1), R₂=H, CH₃, CF₃, C₂F₅ wherein when A==—NO₂,or —C(CN)C(CN)₂, then X₁, X₂, X₃, X₄ are each independently selectedfrom the group —F and —H, and at least one —F is selected, and whenA=—N═C(R1)(R2), wherein R₁=CF₃, C₂F₅, C_(n)F_(2n+1), R₂=H, CH₃, CF₃,C₂F₅, then X₁, X₂, X₃, X₄ are each independently selected from the group—F and —H; or second substituted anilines,

 Wherein D=donor=—NH₂, —N(CH₃)₂, —N(CH₂CH₃)₂, or —N(Y)₂ where Y=alkylalcohols, alkyl (hydrocarbon or fluorocarbon) esters, or alkyl silanederivatives; A₁=primary acceptor=—NO₂, —C(CN)C(CN)₂, or —N═C (R1)(R2),where R₁=CF₃, C₂F₅, C_(n)F_(2n+1), R₂=H, CH₃, CF₃, C₂F₅ A₂=secondaryacceptor=—CN, or —CF₃ wherein X₁, X₂, X₃ are each independently selectedfrom the group —F and —H; and wherein A₁ can be the same as A₂, whereintwo identical or different acceptors may be selected from group A1 ortwo identical or different acceptors may be selected from group A₂, sothat when acceptors are selected from —NO₂, —C(CN)C(CN)₂, —CN, or —CF₃,then X₁, X₂, X₃ are each independently selected from the group —F and—H, and at least one —F is selected; and if at least one acceptor isselected as —N═C (R1)(R2), where R₁=CF₃, C₂F₅, C_(n)F_(2n+1), R₂=H, CH₃,CF₃, C₂F₅, then X₁, X₂, X₃ independently selected from the group —F and—H.
 28. A functional optical material for use in an optical system,comprising: (a) a polymer selected from the group comprising, (1) athermoplastic polymer; (2) a thermosetting polymer; and (3) acombination of thermoplastic and thermosetting polymers; wherein saidthermoplastic and/or thermosetting polymers contain carbon-hydrogenand/or carbon-fluoride functionality; and (b) one or more opticallyactive chromophores blended and/or copolymerized with said polymer,wherein said chromophore comprises: first substituted azobenzenes

 Wherein D=donor=—NH₂, —N(CH₃)₂, —N(CH₂CH₃)₂, or —N(Y)₂ where Y=alkylalcohols, alkyl (hydrocarbon fluorocarbon) esters, or alkyl silanederivatives; A=acceptor=—NO₂, —C(CN)C(CN)₂, or —N═C(R1)(R2), whereinR₁=CF₃, C₂F₅, C_(n)F_(2n+1), R₂=H, CH₃, CF₃, C₂F₅ wherein when A══—NO₂,or —C(CN)C(CN)₂, then X₁, X₂, X₃, X₄ are each independently selectedfrom the group —F and —H, and at least one —F is selected, and whenA═—N═C(R1)(R2), wherein R₁=CF₃, C₂F₅, C_(n)F_(2n+1), R₂=H, CH₃, CF₃,C₂F₅, then X₁, X₂, X₃, X₄ are each independently selected from the group—F and —H; or second substituted azobenzenes,

 Wherein D=donor=—NH₂, —N(CH₃)₂, —N(CH₂CH₃)₂, or —N(Y)₂ where Y=alkylalcohols, alkyl (hydrocarbon or fluorocarbon) esters, or alkyl silanederivatives; primary acceptor=—NO₂, —C(CN)C(CN)₂, or —N═C (R1)(R2),where R₁=CF₃, C₂F₅, C_(n)F_(2n+1), R₂=H, CH₃, CF₃, C₂F₅ secondaryacceptor=—CN, or —CF₃ wherein if A₁ and A₂ are both primary acceptorsselected from —NO₂, or —C(CN)C(CN)₂, then X₁, X₂, X₃ are eachindependently selected from —F and —H, but at least one —F must beselected; wherein if A₁ and A₂ are both secondary acceptors selectedfrom —NO₂, or —C(CN)C(CN)₂, then X₁, X₂, X₃ are each independentlyselected from —F and —H, but at least one —F must be selected; whereinif A₁ and/or A₂ are selected from the primary acceptor —N═C (R1)(R2),where R=CF₃, C₂F₅, C_(F) _(2n+1), R₂=H, CH₃, CF₃, C₂F₅, then X₁, X₂, X₃are each independently selected from —F and —H; and wherein if A₁ isselected from any primary acceptor, and A₂ is selected from anysecondary acceptor, then X₁, X₂, X₃ are each independently selected from—F and —H.
 29. A functional optical material for use in an opticalsystem, comprising: (a) a polymer selected from the group comprising,(1) a thermoplastic polymer; (2) a thermosetting polymer; and (3) acombination of thermoplastic and thermosetting polymers; wherein saidthermoplastic and/or thermosetting polymers contain carbon-hydrogenand/or carbon-fluoride functionality; and (b) one or more opticallyactive chromophores blended and/or copolymerized with said polymer,wherein said chromophore comprises: first substituted stilbenes

 Wherein D=donor=—NH₂, —N(CH₃)₂, —N(CH₂CH₃)₂, or —N(Y)₂ where Y=alkylalcohols, alkyl (hydrocarbon fluorocarbon) esters, or alkyl silanederivatives; A=acceptor=—NO₂, —C(CN)C(CN)₂, or —N═C(R1)(R2), whereinR₁=CF₃, C₂F₅, C_(n)F_(2n+1), R₂=H, CH₃, CF₃, C₂F₅ wherein when A══—NO₂,or —C(CN)C(CN)₂, then X₁, X₂, X₃, X₄ are each independently selectedfrom the group —F and —H, and at least one —F is selected, and whenA═—N═C(R1)(R2), wherein R₁=CF₃, C₂F₅, C_(n)F_(2n+1), R₂=H, CH₃, CF₃,C₂F₅, then X₁, X₂, X₃, X₄ are each independently selected from the group—F and —H; or second substituted stilbenes,

 Wherein D=donor=—NH₂, —N(CH₃)₂, —N(CH₂CH₃)₂, or —N(Y)₂ where Y=alkylalcohols, alkyl (hydrocarbon or fluorocarbon) esters, or alkyl silanederivatives; primary acceptor=—NO₂, —C(CN)C(CN)₂, or —N═C (R1)(R2),where R₁=CF₃, C₂F₅, C_(n)F_(2n+1), R₂=H, CH₃, CF₃, C₂F₅ secondaryacceptor=—CN, or —CF₃ wherein if A₁ and A₂ are both primary acceptorsselected from —NO₂, or —C(CN)C(CN)₂, then X₁, X₂, X₃ are eachindependently selected from —F and —H, but at least one —F must beselected; wherein if A₁ and A₂ are both secondary acceptors selectedfrom —NO₂, or —C(CN)C(CN)₂, then X₁, X₂, X₃ are each independentlyselected from —F and —H, but at least one —F must be selected; whereinif A₁ and/or A₂ are selected from the primary acceptor —N═C (R1)(R2),where R₁=CF₃, C₂F₅, C_(F) _(2n+1), R₂=H, CH₃, CF₃, C₂F₅, then X₁, X₂, X₃are each independently selected from —F and —H; and wherein if A₁ isselected from any primary acceptor, and A₂ is selected from anysecondary acceptor, then X₁, X₂, X₃ are each independently selected from—F and —H.
 30. A functional optical material for use in an opticalsystem, comprising: (a) a polymer selected from the group comprising,(1) a thermoplastic polymer; (2) a thermosetting polymer; and (3) acombination of thermoplastic and thermosetting polymers; wherein saidthermoplastic and/or thermosetting polymers contain carbon-hydrogenand/or carbon-fluoride functionality; and (b) one or more opticallyactive chromophores blended and/or copolymerized with said polymer,wherein said chromophore comprises: first substituted imines,

 Wherein D=donor=—NH₂, —N(CH₃)₂, —N(CH₂CH₃)₂, or —N(Y)₂ where Y=alkylalcohols, alkyl (hydrocarbon fluorocarbon) esters, or alkyl silanederivatives; A=acceptor=—NO₂, —C(CN)C(CN)₂, or —N═C(R1)(R2), whereinR₁=CF₃, C₂F₅, C_(n)F_(2n+1), R₂=H, CH₃, CF₃, C₂F₅ wherein when A==—NO₂,or —C(CN)C(CN)₂, then X₁, X₂, X₃, X₄ are each independently selectedfrom the group —F and —H, and at least one —F is selected, and whenA=—N═C(R1)(R2), wherein R₁=CF₃, C₂F₅, C_(n)F_(2n+1), R₂=H, CH₃, CF₃,C₂F₅, then X₁, X₂, X₃, X₄ are each independently selected from the group—F and —H; or second substituted imines,

 Wherein D=donor=—NH₂, —N(CH₃)₂, —N(CH₂CH₃)₂, or —N(Y)₂ where Y=alkylalcohols, alkyl (hydrocarbon or fluorocarbon) esters, or alkyl silanederivatives; primary acceptor=—NO₂—C(CN)C(CN)₂, or —N═C (R1)(R2), whereR₁=CF₃, C₂F₅, C_(n)F_(2n+1), R₂=H, CH₃, CF₃, C₂F₅ secondaryacceptor=—CN, or —CF₃ wherein if A₁ and A₂ are both primary acceptorsselected from —NO₂, or —C(CN)C(CN)₂, then X₁, X₂, X₃ are eachindependently selected from —F and —H, but at least one —F must beselected; wherein if A₁ and A₂ are both secondary acceptors selectedfrom —NO₂, or —C(CN)C(CN)₂, then X₁, X₂, X₃ are each independentlyselected from —F and —H, but at least one —F must be selected; whereinif A₁ and/or A₂ are selected from the primary acceptor —N═C (R1)(R2),where R₁=CF₃, C₂F₅, C_(n)F_(2n+1), R₂=H, CH₃, CF₃, C₂F₅, then X₁, X₂, X₃are each independently selected from —F and —H; and wherein if A₁ isselected from any primary acceptor, and A₂ is selected from anysecondary acceptor, then X₁, X₂, X₃ are each independently selected from—F and —H.
 31. A functional optical material for use in an opticalsystem, comprising: (a) a polymer selected from the group comprising,(1) a thermoplastic polymer; (2) a thermosetting polymer; and (3) acombination of thermoplastic and thermosetting polymers; wherein saidthermoplastic and/or thermosetting polymers contain carbon-hydrogenand/or carbon-fluoride functionality; and (b) one or more opticallyactive chromophores blended and/or copolymerized with said polymer,wherein at least one chromophore comprises:


32. A functional optical material for use in an optical system,comprising: (a) a polymer selected from the group comprising, (1) athermoplastic polymer; (2) a thermosetting polymer; and (3) acombination of thermoplastic and thermosetting polymers; wherein saidthermoplastic and/or thermosetting polymers contain carbon-hydrogenand/or carbon-fluoride functionality; and (b) one or more opticallyactive chromophores blended and/or copolymerized with said polymer,wherein at least one chromophore comprises:


33. A functional optical material useful in an optical systemcomprising: a polymer of (a) one or more partially or fully fluorinatedfirst monomer(s) having a refractive index of less than about 1.5, orwherein a homopolymer formed from said first monomer(s) has a refractiveindex of less than about 1.5; (b) zero, one, or more second monomer(s)having a refractive index≧1.5, or wherein a homopolymer formed from saidsecond monomer(s) has a refractive index≧1.5; (c) at least one opticallyactive chromophore; (d) at least one compatibilizer for said opticallyactive chromophore; (e) at least one adhesion promoter, having one ormore pendant groups selected from the group consisting of nitrites,silanes, fluorinated silanes, organic acids; fluorinated organic acids,alcohols, fluorinated alcohols, amides, and amines; wherein when acompatibilizer with one particular pendant group is selected, anadhesion promoter with a different pendant group is selected.
 34. Amethod of forming a functional optical material comprising: A.determining if a low index of refraction material (n<1.5) or high indexof refraction material (n≧1.5) is desired, B. for a low refractive indexoptical material (1) selecting one or more monomers having a low indexof refraction; (2) selecting zero, one, or more monomers having a highindex of refraction, wherein the concentration of the monomer(s) with ahigh index of refraction is less than the concentration of monomer(s)having a low index of refraction; (3) selecting zero, one or moreoptically active chromophores; (4) selecting zero, one, or more ofconventional optical chromophores, with the proviso that at least onechromophore must be selected; (5) selecting one or more compatibilizersfor the selected chromophore(s), having one or more pendant groupsselected from the group consisting of nitrites, esters, aromatics;fluorinated esters, and fluorinated aromatics; and (6) selecting one ormore adhesion enhancers, having one or more pendant groups selected fromthe group consisting of nitriles, silanes, fluorinated silanes, organicacids; fluorinated organic acids, alcohols, fluorinated alcohols,amides, and amines; wherein when a compatibilizer with one particularpendant group is selected, an adhesion promoter with a different pendantgroup is selected; and (7) mixing and reacting said selected monomer(s),chromophore(s), compatibilizer, and adhesion enhancer; C. for a highrefractive index optical material (1) selecting one or more monomershaving a high index of refraction; (2) selecting zero, one, or moremonomers having a low index of refraction, wherein the concentration ofthe monomer(s) with a low index of refraction is less than theconcentration of monomer(s) having a high index of refraction; (3)selecting zero, one or more optically active chromophores; (4) selectingzero, one, or more of conventional optical chromophores, with theproviso that at least one chromophore must be selected; (5) selectingone or more compatibilizers for the selected chromophore(s), having oneor more pendant groups selected from the group consisting of nitrites,esters, aromatics; fluorinated esters, and fluorinated aromatics; and(6) selecting one or more adhesion enhancers, having one or more pendantgroups selected from the group consisting of nitrites, silanes,fluorinated silanes, organic acids ????; fluorinated organic acids,alcohols, fluorinated alcohols, amides, and amines; wherein when acompatibilizer with one particular pendant group is selected, anadhesion promoter with a different pendant group is selected; and (7)mixing and reacting said selected monomer(s), chromophore(s),compatibilizer, and adhesion enhancer.
 35. The method according to claim34, wherein high T_(g) materials are prepared by selecting and reactingfluorinated monomers with nonfluorinated monomers.
 36. A functionaloptical material for use in an optical system comprising:

wherein x₁=50-80 wt. %, x₂=10-15 wt. %, X₃=1-5 wt. %, x₄=5-20 wt. % andwherein one or more of said —F atoms may be substituted by an —H atom.37. A compound comprising:


38. A compound comprising: